Pendant-Type Helicene Oligomers with p-Phenylene

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Pendant-Type Helicene Oligomers with p-Phenylene Ethynylene Main Chains: Synthesis, Reversible Formation of Ladderlike Bimolecular Aggregates, and Control of Intramolecular and Intermolecular Aggregation Nozomi Saito, Yutaro Kondo, Tsukasa Sawato, Masanori Shigeno, Ryo Amemiya, and Masahiko Yamaguchi J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b00824 • Publication Date (Web): 07 Jul 2017 Downloaded from http://pubs.acs.org on July 7, 2017

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The Journal of Organic Chemistry

Pendant-Type Helicene Oligomers with p-Phenylene Ethynylene Main Chains: Synthesis, Reversible Formation of Ladderlike Bimolecular Aggregates, and Control of Intramolecular and Intermolecular Aggregation

Nozomi Saito, Yutaro Kondo, Tsukasa Sawato, Masanori Shigeno, Ryo Amemiya, and Masahiko Yamaguchi* Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aoba, Sendai 980-8578, Japan *E-mail: [email protected], Fax: (+81) 22-795-6811

Abstract Pendant-type (P)-helicene oligomers with p-phenylene ethynylene main chains up to a tetramer were synthesized by a building block method. The (P)-tetramer reversibly formed a ladderlike bimolecular aggregate upon cooling and disaggregated upon heating in trifluoromethylbenzene. Two bis(tetramer)s, in which two (P)-tetramers were connected by hexadecamethylene linkers, were also synthesized. The head-to-tail bis(tetramer) formed an intramolecular aggregate, and the head-to-head bis(tetramer) formed an intermolecular aggregate in toluene. The results suggest the antiparallel aggregation structure of the pendant-type (P)-tetramers. The structure of the linker was proven to be effective in controlling intramolecular and intermolecular aggregations. 1 ACS Paragon Plus Environment


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Introduction DNA and RNA are biological oligomers and polymers possessing poly(phosphoryl ester) main chains to which nitrogen-containing heteroaromatic bases are attached as pendant groups. They form ladderlike helical duplexes by noncovalent interactions between complementary base pairs in the pendant groups and carry genetic information, the expression of which is deeply related to the reversible transition between the monomeric strands and the duplexes.1 It is therefore an intriguing subject to synthesize oligomers and polymers with pendant-type aromatic structures and study the reversible formation of ladderlike bimolecular aggregates by noncovalent bonds. Differently from linear compounds in which interacting groups are incorporated in the main chains (Figure 1a), pendant-type oligomers and polymers form ladderlike duplexes by noncovalent interactions between complementary pairs of pendant groups; a ladderlike helical duplex, such as DNA, is in this category (Figure 1b). Ladderlike aggregates and assemblies formed by noncovalent bonds have also been reported,2,3 but no reversible transitions between aggregates and monomers have been observed. Herein we report the synthesis of pendant-type helicene oligomers with p-phenylene ethynylene main chains, their formation of ladderlike bimolecular aggregates, and the reversible transitions between the bimolecular aggregates and the monomers.

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Figure 1. Duplex formation of (a) linear and (b) pendant-type aromatic oligomers and polymers. During the course of our studies on the synthesis and function of linear helicene oligomers,4 we synthesized (P)-ethynylhelicene oligomers (P)-1, in which helicene and m-phenylene were connected by acetylene linkers (Figure 2). The linear helicene oligomers formed double helices5,6 in solution, which exhibited various responses to changes in the environment.7 In this study, an isomeric derivative, (P)-2, in which (P)-helicene pendants were attached to the main chain of p-phenylene ethynylene, was synthesized. The molecular structure of (P)-2 (Figure 2) was designed considering following points. The p-phenylene ethynylene structure was selected as the main chain to provide a space sufficient for locating helicene pendants. In this structure, the distance between the helicene pendants was estimated to be 0.68 nm,8c which seemed sufficient for locating another helicene pendant between them considering a typical π-π stacking distance, 0.34–0.35 nm.9 The helicene pendants were attached to the p-phenylene ethynylene main chain by acetylene linkers, which provide flexibility to the conformation of the helicene pendants. The (P)-helicene pendant oligomer (P)-2 is formally an isomeric form of the (P)-ethynylhelicene oligomer (P)-1. It was then interesting to compare the aggregation behavior of (P)-2 with that of (P)-1. The pendant-type (P)-helicene oligomers (P)-2 were expected to exhibit aggregation properties different from the linear oligomer (P)-1: It was assumed that (P)-2 (n = 4) would form a ladderlike bimolecular aggregate because of its rigid structure. As expected, this study showed that the (P)-tetramer (P)-2 (n = 4) formed bimolecular aggregates in solution.



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Figure 2. Linear and pendant-type helicene oligomers (P)-1 and (P)-2, respectively.

One of notable features of the pendant-type oligomer (P)-2 is the head/tail directionality in its main chain (Figure 2), because the helicene pendants are attached to the main chain at an angle of approximately 60 °, not perpendicularly. The m-(helicenylethynyl)phenyl group is referred to as the head, and the o-(helicenylethynyl)phenyl group, the tail, in this study (Figure 2). When (P)-2 molecules form a ladderlike bimolecular aggregate in which a helicene pendant will be sandwiched by other helicene pendants, parallel and antiparallel arrangements are conceivable (Figure 3a). In contrast, main chains of linear oligomers are generally symmetric in direction, which accordingly does not bring about any difference between parallel and antiparallel arrangements of the bimolecular aggregate. It is also an interesting subject to determine which arrangement, parallel or antiparallel, is formed by (P)-2. The parallel arrangement seems to result in unfavorable π-π interactions between the helicene pendants, and the antiparallel arrangement is anticipated to predominate, as is observed with DNA and RNA.


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Figure 3. Aggregation of pendant-type helicene oligomers. (a) Dimeric aggregation of (P)-2 with parallel and antiparallel arrangements; (b) intramolecular aggregation of head-to-tail bis(tetramer) (P)-3 with antiparallel arrangement; (c) intermolecular aggregation of head-to-head bis(tetramer) (P)-4 with antiparallel arrangement.

To confirm the predominance of the antiparallel arrangement, bis(tetramer)s (P)-3 and (P)-4 were designed, in which two (P)-tetramers (P)-2 (n = 4) were connected by alkyl linkers in a head-to-head and head-to-tail manner, respectively (Figure 4). When the antiparallel arrangement is predominant, the head-to-tail bis(tetramer) (P)-3 would form intramolecular aggregates, and the head-to-head bis(tetramer) (P)-4 would form intermolecular aggregates, because the intramolecular aggregation of (P)-4 would be unfavorable owing to the small length of the linker (Figures 3b and c). As will be discussed below, the results shown in this study are consistent with this assumption. Namely, utilization of bimolecular aggregates with antiparallel arrangements can be a useful method to control intra- and intermolecular aggregations.



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Head

Tail R

OMe

MeO 2C

R R

CO 2Me

MeO 2C

R R 3

2.7 nm

CO 2Me

CO 2

3

CO 2 (CH 2)16 O 2C 3.0 nm

Head

Tail

R= CO 2(n-C10H 21)

(P)-3 Tail

Tail

OMe

MeO 2C

OMe

MeO 2C

R MeO 2C

R MeO 2C

R 3

R 3

2.7 nm

CO 2 Head

(CH 2)16 3.0 nm (P)-4

O 2C Head R= CO 2(n-C10H 21)

Figure 4. Head-to-tail and head-to-head pendant-type helicene bis(tetramer)s (P)-3 and (P)-4.

Results and discussion Synthesis Pendant-type (P)-helicene oligomers with the p-phenylene ethynylene main chains up to the (P)-tetramer (P)-2 (n = 4) were synthesized using a building block (P)-5 (Schemes 1, 4, and 5). A monomer helicene unit was coupled with (P)-5 by the Sonogashira reaction, which was followed by desilylation. The sequence of the reactions efficiently provided the trimer and tetramer (P)-2 (n = 3 and 4).


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Scheme 1. Synthesis of (P)-2 (n = 2, 3, and 4).

The linked (P)-tetramers (P)-3 with the head-to-tail structure were synthesized by the stepwise coupling of two (P)-tetramer groups. A hydroxy derivative (P)-6 was synthesized to attach a linker 7 (Scheme 9) at the tail region, which proceeded from a tetrahydropyranyl (THP)-protected monomer unit (Scheme 6). A sequence of the Sonogashira coupling and deprotection followed by THP removal gave (P)-6 (Scheme 7, 8). Then esterification of (P)-7 with (P)-6 provided (P)-8, which was coupled with the deprotected (P)-2 (n = 4) giving (P)-3 (Scheme 2).



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Scheme 2. Synthesis of head-to-tail bis(tetramer) (P)-3.

Synthesis of the head-to-head bis(tetramer) (P)-4 was more straightforward. The (P)-tetramer (P)-2 (n = 4) was desilylated and coupled with the linker compound 9 by the Sonogashira reaction (Scheme 3).

Scheme 3. Synthesis of head-to-head bis(tetramer) (P)-4.

Bimolecular aggregation of (P)-2 8 ACS Paragon Plus Environment

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(P)-2 (n = 3 and 4) were at the dissociated states in chloroform. Circular dichroism (CD) and UV-Vis analyses (chloroform, 0.5 mM, 25 °C) of (P)-2 (n = 3 and 4) showed monotonic increases in the intensity of the Cotton effect and in absorption (Figure S1a). The structure of the (P)-tetramer (P)-2 (n = 4) was analyzed in chloroform. CD spectra (chloroform, 0.5 mM, 25 °C) gave positive maxima at 334 and 425 nm and a negative maximum at 373 nm (Figure 5a, top). The strong cotton effect indicated the formation of an ordered structure. The UV-Vis spectrum showed absorption maxima at 321 and 380 nm (Figure 5a, bottom), which was ascribed to the aggregation by the π-π interactions. Fluorescence analysis (chloroform, 0.15 mM, 25 °C) of (P)-2 (n = 4) revealed an emission with the maximum at 466 nm on excitation at 365 nm (Figures 5b and S1b), which supported the aggregate formation. Vapor pressure osmometry (VPO) analysis (chloroform, 1.0 mM, 35 °C) of (P)-2 (n = 4) indicated the presence of monomers, (2.5 ± 0.1) × 103; calcd. 2587. Dynamic light scattering (DLS) analysis (chloroform, 0.5 mM, 25 °C) indicated an average diameter of the particles in solution to be 2.0 nm (Figure S1c), which showed molecular aggregation and not higher assembly.



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Figure 5. (a) CD (top) and UV-Vis (bottom) spectra (0.5 mM, 25 °C) and (b) fluorescence spectra (0.15 mM, 25 °C) of (P)-2 (n = 4) in chloroform and trifluoromethylbenzene. The fluorescence spectra were obtained by excitation at 365 nm. The spectra were obtained after being settled under each condition for 20 min.

The (P)-tetramer (P)-2 (n = 4) formed a bimolecular aggregate in trifluoromethylbenzene. CD spectra (trifluoromethylbenzene, 0.5 mM, 25 °C) of (P)-2 (n = 4) showed enhanced Cotton effects with positive maxima at 330 and 425 nm than those in chloroform as well as the negative maxima at 307 and 365 nm, which were accompanied by a positive maximum with low intensity around 480 10 ACS Paragon Plus Environment

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nm (Figure 5a, top) not observed in chloroform. UV-Vis spectra (trifluoromethylbenzene, 0.5 mM, 25 °C) of (P)-2 (n = 4) showed a new absorption maximum at 450 nm (Figure 5b, bottom). Fluorescence emission (trifluoromethylbenzene, 0.15 mM, 25 °C) was observed at 514 nm, which shifted

to

a

longer

wavelength

from

466

nm

in

chloroform

(Figure

5b).

VPO

(trifluoromethylbenzene, 1.0 mM, 40 °C) analysis indicated the presence of dimers (5.5 ± 0.1) × 103; calcd. 5174. DLS analysis (trifluoromethylbenzene, 0.5 mM, 25 °C) indicated an average diameter of 2.9 nm for the particles in solution (Figure S3).

1

H-NMR spectra in

trifluoromethylbenzene were considerably broadened (Figure S4) compared with those in CDCl3 (Figure S2), which indicated aggregate formation. Those results indicated that (P)-2 (n = 4) formed a bimolecular aggregate in trifluoromethylbenzene. Formation of the bimolecular aggregate was reversible in response to thermal stimuli. The Δε value at 325 nm in CD spectra (trifluoromethylbenzene, 0.5 mM) of (P)-2 (n = 4) decreased upon heating at 70 °C and increased upon cooling at 25 °C (Figure 6). The change of the Δε was reproducible. The results indicated that (P)-2 (n = 4) reversibly aggregated upon cooling and disaggregated upon heating.

Figure 6. The Δε value at 325 nm in CD spectra (trifluoromethylbenzene, 0.5 mM) of (P)-2 (n = 4) at 70 and 25 °C. The Δε values were obtained after being settled under each condition for 20 min.



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Solvent effects on aggregation were examined (Figure S5), and an enhancement of the CD intensity was observed in trifluoromethylbenzene but not in toluene, chlorobenzene, and 1,3-difluorobenzene. CD and UV-Vis analyses were conducted at different temperatures and concentrations of (P)-2 (n = 4) in trifluoromethylbenzene (Figures 7, S6, and S7). When the temperature of the solution (0.5 mM) was changed between 5 and 70 °C, the CD intensity of the positive maxima at 330 and 425 nm increased upon cooling, and a small change occurred in the negative maxima (Figure 7a, top). UV-Vis spectra gave absorption maxima at 316 and 380 nm and showed an increase in the absorbance at 450 nm upon cooling (Figure 7a, bottom). Comparison of the CD spectra (1 mM) at 5, 15, and 25 °C showed convergence to a single spectrum (Figure S6a), which was determined to be S-associated state, at which the equilibrium shifted to the aggregated state essentially without containing (P)-2 at the dissociated state. The CD spectra (0.02 mM) at 50 and 70 °C converged to a spectrum with a Δε value of −10 cm−1M−1 at 411 nm (Figure S6d), which was determined to indicate the S-dissociated state, containing (P)-2 only at the dissociated state.


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Figure 7. (a) Effect of temperature on CD (top) and UV-Vis (bottom) spectra of (P)-2 (n = 4) (trifluoromethylbenzene, 0.5 mM). (b) Effect of concentration on CD (top) and UV-Vis (bottom) spectra of (P)-2 (n = 4) (trifluoromethylbenzene, 30 °C). The spectra were obtained after being settled at each temperature for 20 min.

The binding constant K at temperatures between and 25 and 70 °C was determined by curve fitting optimization using the Δε value −10 cm−1M−1 at 411 nm of the S-dissociated state (Figure S8 and Table S1). The van’t Hoff analysis using K at temperatures between 5 and 70 °C provided ΔH = −65 kJmol−1 and ΔS = −0.19 kJmol−1K−1 (Figure S9). The results described above indicated that the pendant-type helicene oligomers (P)-2 (n = 4) formed a bimolecular aggregate in solution, most probably a ladderlike duplex. The large change in the fluorescence spectra between the associated and dissociated states is consistent with the π-stacking structure of the aggregates, which is supported by the 1H-NMR spectra showing broad peaks corresponding to the aggregates. Considering the chiral structure of (P)-2 and the enhancement of CD upon aggregation, the ladderlike duplex may be loosely helical. It should be 13 ACS Paragon Plus Environment


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noted that the (P)-tetramer (P)-2 (n = 4) reversibly formed a ladderlike bimolecular aggregate upon cooling and disaggregated upon heating, which was enabled by the noncovalent π-π interaction connecting two compounds. Considering the solvent effects on the pendant-type (P)-2 similar to that of the linear (P)-1, similar driving force, nonplanar π-π interactions,6 may be involved in the aggregations of them. A notable difference, however, appeared in the aggregation of linked compounds, which is discussed below.

Intramolecular aggregation of head-to-tail bis(tetramer) (P)-3 As noted in the introduction, the bimolecular aggregation of the pendant-type helicene oligomer (P)-2 is considered to have a ladderlike structure in which a helicene pendant is sandwiched by other helicene pendants, and two compounds are considered to be arranged in an antiparallel manner. The head-to-tail bis(tetramer) (P)-3 would then predominate in intramolecular aggregation over intramolecular aggregation. The aggregation of the head-to-tail bis(tetramer) (P)-3 was examined. It was initially confirmed that (P)-3 dissociated in chloroform (Figure 8). The CD and UV-Vis spectra (chloroform, 0.2 mM, 25 °C) of (P)-3 were similar to those of (P)-2 (n = 4) in chloroform (Figures S1a and S10): CD gave positive maxima at 334 and around 425 nm as well as a negative maximum at 373 nm, and UV-Vis gave absorption maxima at 321 and 380 nm. The fluorescence spectrum (chloroform, 0.1 mM, 25 °C) showed emission at 474 nm (Figure 8b), which was consistent with the dissociated state. VPO (chloroform, 1.0 mM, 35 °C) analysis of (P)-3 indicated the monomeric state (5.4 ± 0.1) × 103; calcd. 5767. DLS analysis (chloroform, 0.2 mM, 25 °C) indicated an average diameter of 3.7 nm (Figure S11).


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Figure 8. (a) CD (top), UV-Vis (bottom), and (b) fluorescence spectra of (P)-3 in chloroform (0.1 mM, 5 °C) and toluene (0.5 mM, 5 °C). The fluorescence spectra were obtained by excitation at 365 nm. The spectra were obtained after being settled under each condition for 20 min.

Toluene was used as the solvent to examine the aggregation of (P)-3, because complex phenomena were observed in trifluoromethylbenzene, supposedly because of the formation of higher-order aggregates. CD (0.5 mM, 25 °C, toluene) spectra showed Cotton effects with positive maxima at 333 and 433 nm and negative maxima at 320 and 373 nm (Figure 8a, top). UV-Vis (0.5 15 ACS Paragon Plus Environment


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mM, 25 °C) spectra showed the absorption maxima at 320 and 383 nm accompanied by a shoulder around 450 nm at lower temperatures for (P)-2 (n = 4) (Figure 8a, bottom). Fluorescence analysis (toluene, 5 °C, 0.5 mM) showed emission at 510 nm, which is characteristic of the associated state (Figures 8b and S12). VPO analysis (toluene, 40 °C) at 1.0 mM provided (5.9 ± 0.1) × 103; calcd. 5767, which represented the monomeric nature. The average diameter determined by DLS analysis (toluene, 5 °C, 0.2 mM) was 4.0 nm (Figure S13), which indicated no higher aggregation. The results indicated the intramolecular aggregation of (P)-3 in toluene. CD and UV-Vis analyses of (P)-3 were conducted at different temperatures in toluene (Figure S14). When the temperature was changed from 5 to 70 °C at 0.5 mM, the CD intensity decreased, which indicated dissociation (Figures 9a and S14b, top). The UV-Vis intensity at 450 nm decreased upon heating to 70 °C (Figures 9a and S14b, bottom). The results indicated dissociation by heating. It was noted that CD and UV-Vis spectra showed very small changes at concentrations between 0.5 and 0.005 mM (Figures 9b and S15). The absence of a concentration effect supported the intramolecular nature of the aggregation. Intramolecular aggregation predominated over intermolecular aggregation for the head-to-tail bis(tetramer) (P)-3, which is consistent with our previous observation of linked oligomers with flexible linking groups.8


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Figure 9. (a) Effect of temperature on CD (top) and UV-Vis (bottom) spectra of (P)-3 (toluene, 0.5 mM). (b) Effect of concentration on CD (top) and UV-Vis (bottom) spectra of (P)-3 (toluene, 5 °C). The spectra were obtained after being settled at each temperature for 20 min.

Intermolecular aggregation of head-to-head bis(tetramer) (P)-4 The head-to-head bis(tetramer) (P)-4 is expected to form the intermolecular aggregation predominant over the intramolecular aggregation. It was confirmed that the head-to-head bis(tetramer) (P)-4 dissociated in chloroform. The shapes of CD and UV-Vis spectra (chloroform, 0.2 mM, 25 °C) (Figures 10a and S16a) were similar to those of (P)-2 (n = 4) (Figure 5a) and (P)-3 (Figure 8a) in chloroform (Figure S16b): CD gave positive maxima at 334 and 426 nm as well as negative maxima at 315 and 373 nm, and UV-Vis showed an absorption maximum at 322 and 382 nm. The fluorescence spectrum (chloroform, 0.5 mM, 25 °C) gave the emission maximum at 476 nm (Figure 10b). VPO analysis (chloroform, 1.0 17 ACS Paragon Plus Environment


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mM, 30 °C) of (P)-4 indicated the monomeric state, (5.4 ± 0.1) × 103; calcd. 5767. DLS analysis (chloroform, 0.1 mM, 25 and 40 °C) provided an average diameter of 1.7 nm (Figure S17). The aggregation of (P)-4 was examined in toluene. The CD spectra (toluene, 0.5 mM, 25 °C) showed positive maxima at 333 and 431 nm and negative maxima at 315 and 371 nm (Figure 9a, top), as was observed for (P)-2 (n = 4) (Figure 5a) and (P)-3 (Figure 8a). UV-Vis spectra (toluene, 0.5 mM, 25 °C) showed absorption maxima at 320 and 382 nm with a shoulder at 450 nm, which were characteristic of the aggregated state (Figures 10a, bottom). The fluorescence spectrum (toluene, 0.5 mM, 25 °C) showed an emission at 516 nm with a shoulder around 550 nm (Figure 10b). VPO analysis (toluene, 40 °C) at 2.0 mM indicated an aggregated state (8.1 ± 0.1) × 103; calcd. 11534. DLS analysis (25 °C) using 0.05 mM, 0.1 mM, and 0.2 mM solutions showed small changes with average diameters of 3-4 nm (Figures S19 and S20), which are larger than those in chloroform. The results indicated the intermolecular aggregation of (P)-4 in this solvent.


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Figure 10. (a) CD (top) and UV-Vis (bottom) spectra of (P)-4 in chloroform (0.2 mM, 25 °C) and toluene (0.5 mM, 25 °C). (b) Fluorescence spectra of (P)-4 in chloroform (0.5 mM, 5 °C) and toluene (0.5 mM, 5 °C). The fluorescence spectra were obtained by excitation at 365 nm. The spectra were obtained after being settled under each condition for 20 min.

CD and UV-Vis analyses were conducted at different temperatures and concentrations of (P)-4 in toluene (Figures 11, S21, and S22). The CD intensity at 431 nm decreased with heating from 5 to 70 °C at 0.5 mM, and the UV-Vis intensity at 450 nm also decreased on heating to 70 °C (Figure 11a). These results indicated dissociation by heating. The CD analyses upon decreasing concentrations from 0.5 to 0.05 mM showed decreases in CD intensity at temperatures below 30 °C (Figures 11b and S22f-h), which indicated dissociation at lower concentrations. Aggregation did not occur at 0.005 mM. Substantial concentration effects on the spectra indicated the intermolecular aggregation of (P)-1 in toluene. It is notable that the intermolecular aggregation of (P)-4 occurred despite the incorporation of the flexible linker. The intramolecular aggregation of (P)-3 and intermolecular aggregation of (P)-4 was supported by the diffusion coefficient D obtained by DOSY experiment (toluene-d8, 0.5 mM, 5 °C): (P)-3, D 0.635 × 108 m2s−1; (P)-4, D 0.477 × 108 m2s−1. A smaller diffusion coefficient D for (P)-4 is consistent with larger size of the aggregate (Table S2).



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Figure 11. (a) Effect of temperature on CD (top) and UV-Vis (bottom) spectra of (P)-4 (toluene, 0.5 mM). (b) Effect of concentration on CD (top) and UV-Vis (bottom) spectra of (P)-4 (toluene, 5 °C). The spectra were obtained after being settled at each temperature for 20 min.

Two intermolecular aggregation modes of (P)-4 are conceivable, in which one of the (P)-2 (n = 4) unit is aggregated (Figure 12a) or two units are aggregated (Figure 12b). The latter may be unlikely because of substantial entropic loss with the formation of the doubly aggregated structure. Our previous work showed that the intramolecular aggregation predominated over the intermolecular aggregation for linked helicene oligomers with flexible linking groups such as hexadecamethylene group.8c This behavior was ascribed to the minimization of the entropic loss in the intramolecular aggregation compared with the intermolecular aggregation. To promote an intermolecular aggregation by linked oligomers, changing the structure of the linker has been proven to be effective, such as the use of a rigid linker: Rigid linkers cannot fold, therefore intramolecular aggregation is inhibited.8 In this study, we developed another method using the 20 ACS Paragon Plus Environment

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antiparallel aggregation to promote the intermolecular aggregation of compounds even with flexible linkers, in which the intramolecular aggregation is inhibited by the unfavorable structure of the antiparallel arrangement. It may be worth noting that, using this methodology, even compounds with flexible linkers can form intermolecular aggregates which outweigh the strong entropic control associated with intermolecular aggregations.

Figure 12. The intermolecular dimeric aggregation of (P)-4 in which (a) one of the tetramer (P)-2 (n = 4) unit is aggregated and (b) two units are aggregated.

Conclusions In summary, the pendant-type helicene oligomers with the p-phenylene ethynylene main chains were synthesized, and (P)-tetramer (P)-2 (n = 4) formed bimolecular aggregates upon cooling and disaggregated upon heating in solution. Ladderlike structure, in which a helicene pendant will be sandwiched by other helicene pendants, with the antiparallel arrangement was suggested. The bis(tetramer)s (P)-3 and (P)-4, which were obtained by connecting (P)-2 (n = 4) with flexible linkers in the head-to-tail and head-to-head manner, exhibited intra- and intermolecular aggregations, respectively. It was shown that structure of the linker was effective in controlling intramolecular and intermolecular aggregations.



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Page 22 of 51

Experimental section General method. Melting points were determined with a Yanaco micro melting point apparatus without correction. Elemental analyses were conducted with a Yanaco CHN CORDER MT-6. Optical rotations were measured on a JASCO P-1010 polarimeter. IR spectra were measured on a JASCO FT/IR-400 spectrophotometer. 1H NMR (400 MHz) spectra were recorded on a Varian Vnmr J2.2C with tetramethylsilane as an internal standard.

13

C NMR spectra were recorded on a

Varian Vnmr J2.2C (100 MHz) and were referenced to the residual solvents CDCl3 (δ 77.0). Chemical shifts are expressed in parts per million (ppm, δ). The abbreviations of signal patterns are as follows: s, singlet; d, doublet; t, triplet; q, quartet; q, quintet. Diffusion ordered two-dimensional NMR spectroscopy (DOSY) were recorded on JEOL ECA-700. Low- and High- resolution mass spectra were recorded on a JEOL JMS-DX-303, JEOL JMS-700, or a JEOL JMS-T 100GC. FAB mass spectra were recorded on a JEOL JMS-700 spectrometer by using m-nitrobenzyl alchohol matrix. MALDI-TOF MS spectra were recorded on a Shimadzu AXIMA Assurance using α-cyano-4-hydroxycinnamic acid as the matrix. CD and UV-Vis spectra were measured on a JASCO J-720 spectropolarimeter. The path length 0.0107 cm of quartz round cell and 0.0217 cm of quartz square cell were used. Fluorescent spectra were obtained uing a JACSCO FP-6500 spectrofluorometer. Dynamic light scattering (DLS) determined at 173° scattering angle was observed by a Zetasizer Nano S. Vapor pressure osmometry (VPO) was conducted with KNAUER K-7000 molecular weight apparatus using benzil as a standard. Gel permeation chromatography (GPC) was conducted with Recycling Preparative HPLC LC-908 or LC-918 (Japan Analytical Industry, Co. Ltd.).

Decyl 4-iodo-2,5-dimethyloxybenzoate, 10 Under an argon atmosphere, a solution of 1,4-dimethyloxy-3-iodobenzoic acid (3.3 g, 10.8 mmol) 22 ACS Paragon Plus Environment

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and potassium carbonate (3.0 g 21.6 mmol) in N,N-dimethylformamide (33 mL) was stirred at room temperature for 30 min, and 1-bromodecane (2.3 g, 12.0 mmol) was added. Then, the mixture was stirred at 60 °C for 3 h. The reaction was quenched by adding water, and the organic materials were extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 60:1, 20:1, and 10:1) gave 10 (4.2 g, 9.3 mmol, 87 %) as a colorless solid. Mp 50-51 °C (CHCl3-methanol). LRMS (EI) m/z 448.1 (M+, 100%). HRMS (EI) m/z Calcd. for C19H29IO4 (M+): 448.11105, Found: 448.11142. IR (KBr) 2924, 2849, 1720, 1490, 1210, 764 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.88 (3H, t, J = 6.8 Hz), 1.27-1.45 (14H, m), 1.75 (2H, quint, J = 7.1 Hz), 3.86 (3H, s), 3.87 (3H, s), 4.30 (2H, t, J = 6.6 Hz), 7.24 (1H, s), 7.41 (1H, s) 13

C NMR (100 MHz, CDCl3) δ 13.9, 22.5, 25.8, 28.5, 29.0, 29.1, 29.3, 29.4, 31.7, 56.71, 56.72,

65.1, 91.5, 112.7, 120.6, 124.0, 151.9, 153.3, 165.5. Decyl 2,5-dihydroxy-4-iodobenzoate, 11 Under an argon atmosphere, to a solution of 10 (3.2 g, 7.1 mmol) in dichloromethane (35.0 mL), was added borane tribromide (1 M in dichloromethane) (28.4 ml, 28.4 mmol) at −78 °C. The mixture was warmed to room temperature, and stirred at the temperature for 2 h. The reaction was quenched by adding water, and the organic materials were extracted with dichloromethane. The organic layer was washed with water, brine and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 20:1, and 10:1) gave 11 (2.7 g, 6.4 mmol, 90.4 %) as a colorless oil. LRMS (EI) m/z 420.1 (M+, 59%), 279.9 ([M–C10H20]+, 100%), 261.9 ([M–C10H21–OH]+, 79%). HRMS (EI) m/z Calcd. for C17H25IO4 (M+): 420.0798, Found: 420.0804. IR (KBr) 3120 2923, 1708, 1431, 1208, 1136 cm−1. 1

H-NMR (400 MHz, CDCl3) δ 0.88 (3H, t, J = 7.0 Hz), 1.27-1.44 (14H, m), 1.77 (2H, quint, J = 7.0

Hz), 4.33 (2H, t, J = 6.6 Hz), 4.95 (1H, s), 7.38 (1H, s), 7.41 (1H, s), 10.34 (1H, s).13C NMR (100 MHz, CDCl3) δ 14.1, 22.7, 25.9, 28.5, 29.2, 29.3, 29.48, 29.52, 30.1, 31.9, 65.9, 94.8, 113.6, 126.8, 147.4, 155.2, 169.5. Decyl 4-iodo-2,5-trifluoromethanesulfonyloxybenzoate, 12 Under an argon atmosphere, to a solution of 11 (2.0 g, 4.8 mmol) in dichloromethane (32.0 mL) was added triethylamine (4.0 mL, 28.5 mmol) and trifluoromethanesulfonic anhydride (2,4 mL, 14.3 mmol) at −78 °C. The mixture was warmed to 0 °C, and stirred at the temperature for 3 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with dichloromethane. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by 23 ACS Paragon Plus Environment


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Page 24 of 51

silica gel chromatography (hexane:ethyl acetate = 60:1, 50:1, and 40:1) gave 12 (3.1 g, 4.6 mmol, 96 %) as a colorless solid. Mp 49-50 °C (CHCl3-methanol). LRMS (EI) m/z 684 (M+, 1.1%), 545 ([M–C10H20+H]+, 100%), 527 ([M–OC10H21]+, 72%), 261 ([M–I-2OTf]+, 52%). HRMS (EI) m/z Calcd. for C19H23F6IO8S2 (M+): 683.9783. Found: 683.9783. IR (KBr) 2921, 2851, 1727, 1435, 1214, 1135, 887 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.88 (3H, t, J = 6.8 Hz), 1.27-1.41 (14H, m), 1.78 (2H, quint, J = 7.2 Hz), 4.39 (2H, t, J = 6.8 Hz), 7.83 (1H, s), 7.97 (1H, s). 13C NMR (100 MHz, CDCl3) δ 14.0, 22.6, 25.7, 28.3, 29.1, 29.3, 29.4, 31.8, 67.1, 95.2, 118.6 (q, JC-F = 319.3 Hz), 124.9, 126.6, 134.9, 146.2, 149.5, 161.7. Decyl 2-hydroxy-4-iodo-5-methoxy benzoate, 13 Under an argon atmosphere, to a solution of 10 (0.9 g, 2.1 mmol) in dichloromethane (61.0 mL), was added borane tribromide (1M in dichloromethane) (4.2 mL, 4.2 mmol) at −78 °C. The mixture was warmed to room temperature, and stirred at the temperature for 1 h. The reaction was quenched by adding methanol, and the organic materials were extracted with dichloromethane. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane only, hexane:ethyl acetate = 60:1) gave 13 (0.6 g, 1.4 mmol, 65 %) as a colorless solid. Mp 31-32 °C (CHCl3-methanol). LRMS (EI) m/z 434.1 (M+, 55%), 294 ([M–C10H20]+, 56%), 276 ([M–C10H21– OH]+, 100%). HRMS (EI) m/z Calcd. for C18H27IO4 (M+): 434.0954. Found: 434.0955. IR (KBr) 3148, 2965, 2924, 2851, 1674, 1469, 1262, 1208, 1031, 787 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.88 (3H, t, J = 6.8 Hz), 1.27-1.47 (14H, m), 1.79 (2H, quint, J = 7.1 Hz), 3.85 (3H, s), 4.35 (2H, t, J = 7.0 Hz), 7.16 (1H, s), 7.50 (1H, s), 10.41 (1H, s).

13

C NMR (100 MHz, CDCl3) δ 14.1, 22.7,

25.9, 28.5, 29.2, 29.3, 29.5, 31.9, 56.9, 65.8, 96.1, 109.4, 112.3, 128.7, 151.0, 155.9, 169.6. Decyl 4-iodo-5-methoxy-2-trifluoromethanesulfonyloxybenzoate, 14 Under an argon atmosphere, to a solution of 13 (0.5 g, 1.2 mmol) in dichloromethane (9.2 mL) was added triethylamine (0.4 mL, 2.4 mmol) and trifluoromethanesulfonic anhydride (0.5 ml, 4.71 mmol) at −100 °C. The mixture was warmed to 0 °C, and stirred at the temperature for 30 min. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with dichloromethane. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 60:1) gave 14 (0.7 g, 1.2 mmol, 99 %) as a colorless solid. Mp 49-50 °C (CHCl3-methanol). LRMS (EI) m/z 566.0 (M+, 100%), 425.9 ([M– C10H20]+, 89%), 276.9 ([M–C10H20–OTf]+, 91%). HRMS (EI) m/z Calcd. for C19H26F3IO6S (M+): 566.0447. Found: 566.0433. IR (KBr) 2926, 2855, 1729, 1428, 1211, 1141 cm−1. 1H-NMR (400 24 ACS Paragon Plus Environment

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MHz, CDCl3) δ 0.88 (3H, t, J = 6.8 Hz), 1.26-1.44 (14H, m), 1.79 (2H, quint, J = 7.1 Hz), 3.96 (3H, s), 4.38 (2H, t, J = 7.0 Hz), 7.41 (1H, s), 7.68 (1H, s). 13C NMR (100 MHz, CDCl3) δ 14.1, 22.6, 25.8, 28.3, 29.2, 29.3, 29.4, 29.5, 31.8, 57.0, 66.6, 91.2, 112.4, 118.6 (q, JC-F = 319.8 Hz), 125.5, 133.4, 141.2, 157.8, 163.5. Methyl (P)-8-ethynyl-1,12-dimethylbenzo[c]phenanthrene-5-carboxylate, (P)-15 Under

an

argon

atmosphere,

to

a

solution

of

methyl

1,12-dimethylbenzo[c]phenanthrene-5-formyl-8-carboxylate (1.94 g, 5.41 mmol) in tetrahydrofran (20 mL) and methanol (16 mL) were added potassium carbonate (15.0 g, 108.2 mmol) and dimethyl (1-diazo-2-oxopropyl)phosphonate (2.1 g, 10.8 mmol) at room temperature, and the mixture was stirred at room temperature for 3 h. The reaction was quenched by adding water, and the organic materials were extracted with dichloromethane. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 8:1 and 4:1) gave (M)-6 (1.57 g, 4.64 mmol, 86 %) as a yellow solid. Mp 69-70 °C (CH2Cl2-methanol). [α]27D −275 (c 0.10, CHCl3). LRMS (EI) m/z 338.1 (M+, 100%). HRMS (EI) m/z Calcd. for C24H18O2 (M+): 338.13068. Found: 338.12792. IR (KBr) 3285, 2949, 2925, 2101, 1717, 1241 cm−1. 1H-NMR (400 MHz, CDCl3) δ 1.87 (3H, s), 1.91 (3H, s), 3.56 (1H, s), 4.07 (3H, s), 7.42 (1H, d, J = 7.2 Hz), 7.45 (1H, d, J = 7.2 Hz), 7.65 (1H, dd, J = 7.2, 8.4 Hz), 7.68 (1H, t, J = 7.6 Hz), 8.09 (1H, s), 8.43 (1H, s), 8.45 (1H, d, J = 8.0 Hz), 8.81 (1H, d, J = 8.0 Hz) 13C NMR (100 MHz, CDCl3) δ 23.1, 23.4, 52.4, 81.6, 82.5, 119.5, 123.0, 123.6, 126.8, 127.3, 127.4, 128.9, 129.0, 129.30, 129.31, 129.7, 130.1, 130.6, 130.8, 131.4, 132.8, 136.5, 137.1, 167.8. Building block precursor, (P)-16 Under

an

argon

atmosphere,

a

solution

of

(P)-15

(0.45

g,

1.34

mmol),

tris(dibenzylidenacetone)dipalladium(0) chloroform adduct (38.7 mg, 0.03 mmol), cuprous iodide (79.9 mg, 0.42 mmol), tris(2,4,6-trimethylphenyl)phosphine (78.1 mg, 0.20 mmol),

and

tetrabutylammonium

and

iodide

(1.50

g,

4,02

mmol)

in

trietylamine

(1.0

mL)

N,N-dimethylformamide (16.0 mL) was freeze-evacuated three times. A solution of 12 (1.05 g, 1.54 mmol) in N,N-dimethylformamide (7.0 mL) was freeze-evacuated three times, and was added dropwise to the above mixture. The resulted mixture was stirred at room temperature for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene =4:1, 2:1, and 1:1) gave (P)-16 (1.06 g, 1.18 mmol, 88 %) as a 25 ACS Paragon Plus Environment


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Page 26 of 51

yellow solid. Mp 143-144 °C (CH2Cl2-methanol). [α]27D −380 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C43H41F6O10S2+ ([M+H]+): 895.20. Found: 895.16. Anal. (C43H40F6O10S2) Calcd.: C, 57.71; H, 4.51. Found: C, 57.88; H, 4.55. IR (KBr) 2925, 2854, 2199, 1727, 1429, 1245 cm−1. 1H-NMR(400 MHz, CDCl3) δ 0.89 (3H, t, J = 6.8 Hz), 1.28-1.45 (14H, m), 1.82 (2H, quint, J = 7.1 Hz), 1.90 (3H, s), 1.94 (3H, s), 4.09 (3H, s), 4.43 (2H, t, J = 7.0 Hz), 7.46 (1H, d, J = 7.2 Hz), 7.51 (1H, d, J =7.2 Hz), 7.68 (1H, t, J = 7.8 Hz), 7.68 (1H, s), 7.75 (1H, t, J = 7.6 Hz), 8.08 (1H, s), 8.26 (1H, s), 8.45 (1H, d, J = 7.6 Hz), 8.48 (1H, s), 8.83 (1H, d, J = 8.4 Hz).

13

C NMR (100 MHz, CDCl3) δ 14.1, 22.7, 23.1, 23.4, 25.8, 28.3, 29.2, 29.3, 29.5, 31.9,

52.4, 67.2, 85.7, 99.9, 117.1, 118.1, 120.3, 123.2, 123.3, 124.4, 125.6, 125.7, 127.2, 127.7, 127.76, 127.79, 129.1, 129.3, 129.70, 129.72, 130.0, 130.5, 130.7, 131.4, 132.0, 136.8, 137.4, 146.8, 147.9, 161.8, 167.7. Building block, (P)-5 Under an argon atmosphere, to mixture of tetrakis(triphenylphosphine)dipalladium(0) (43.22 mg, 0.0374 mmol), cuprous iodide (10.68 mg, 0.056 mmol), (P)-16 (121.2 mg, 0.14 mmol) in N,N-dimethylformamide (3 mL), tetrahydrofuran (3 mL), and triethylamine (0.37 mL) was added a solution of trimetylsililacetylene (122 mg, 0.19 mmol) in N,N-dimethylformamide (0.7 mL) and tetrahydrofuran (0.7 mL) over 45 min. The mixture was stirred 45°C for 3 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene = 1:1 to hexane:ethyl acetate = 8:1 to 6:1), and GPC (toluene) gave (P)-5 (36.6 mg, 0.04 mmol, 31 %) as a yellow solid. Mp 145-146 °C (CHCl3-methanol). [α]27D −369 (c 0.10, CHCl3).

MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for

C47H49F3O7SSi (M+): 842.29. Found: 841.67. Anal. (C47H49F3O7SSi) Calcd.: C, 66.96; H, 5.86. Found: C, 67.09; H, 6.13. IR (KBr) 2925, 2854, 2209, 1729, 1716, 1425, 1249, 1214, 1145 cm−1. 1

H-NMR(400 MHz, CDCl3) δ 0.32 (9H, s), 0.89 (3H, t, J = 6.8 Hz), 1.28-1.49 (14H, m), 1.82 (2H,

quint, J = 7.2 Hz), 1.91 (3H, s), 1.94 (3H, s), 4.09 (3H, s), 4.38 (2H, t, J = 7.0 Hz), 7.45 (1H, d, J = 6.8 Hz), 7.50 (1H, d, J = 7.2 Hz), 7.67 (1H,dd, J = 7.2, 8.0 Hz), 7.74 (1H, dd, J = 7.2, 8.0 Hz), 7.94 (1H, s), 8.01 (1H, s), 8.24 (1H, s), 8.49 (1H, s), 8.50 (1H, d, J = 6.9 Hz), 8.83 (1H, J = 8.0 Hz). 13C NMR (100 MHz, CDCl3) δ –0.27, 14.1, 22.6, 23.1, 23.4, 25.9, 28.5, 29.2, 29.3, 29.5, 31.8, 52.4, 66.2, 86.5, 97.6, 100.9, 103.1, 117.1, 118.8, 120.3, 121.8, 123.1, 123.5, 123.6, 123.9, 126.9, 127.6, 129.0, 129.4, 129.5, 129.6, 129.8, 130.3, 130.6, 131.4, 131.4, 132.2, 133.2, 136.6, 137.2, 139.7, 148.1, 164.0, 167.7.


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Precursor of the monomer (P)-2 (n = 1), (P)-17 Under

an

argon

atmosphere,

a

solution

of

(P)-15

(176

mg,

0.45

mmol),

tris(dibenzylidenacetone)dipalladium(0) chloroform adduct (13 mg, 0.011 mmol), cuprous iodide (25.7

mg,

0.14

tetrabutylammonium

mmol), iodide

tris(2,4,6-trimethylphenyl)phosphine (499

mg,

1.35

mmol)

in

(26.2

mg,

triethylamine

0.068 (0.4

mmol),

mL)

and

N,N-dimethylformamide (5.0 mL) was freeze-evacuated three times. A solution of 14 (308 mg, 0.54 mmol) in N,N-dimethylformamide (3.0 mL) was freeze-evacuated three times, and was added to the above mixture. The mixture was stirred for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene = 4:1, 2:1, and 1:1) gave (P)-17 (314 mg, 0.40 mmol, 90 %) as a yellow solid. Mp 235-236 °C (CHCl3-methanol). [α]27D −371 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C43H44F3O8S ([M+H]+): 777.27. Found: 777.89. Anal. (C43H43F3O8S) Calcd.: C, 66.48; H, 5.58. Found: C, 66.82; H, 5.90. IR (KBr) 2925, 2854, 2205, 1722, 1427, 1249, 1208, 1142 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.89 (3H, t, J = 6.8 Hz), 1.24-1.46 (14H, m), 1.83 (2H, quintet, J = 8.0 Hz), 1.90 (3H, s), 1.95 (3H, s), 4.09 (3H, s), 4.10 (3H, s), 4.42 (2H, t, J = 6.8 Hz), 7.45 (1H, d, J = 8.0 Hz), 7.49 (1H, d, J = 8.0 Hz), 7.51 (1H, s), 7.61 (1H, s), 7.67 (1H, t, J = 8.0 Hz), 7.73 (1H, t, J = 8.0 Hz), 8.18 (1H, s), 8.48 (1H, s), 8.58 (1H, d, J = 8.0 Hz), 8.82 (1H, d, J = 8.0 Hz).

13

C

NMR (150 MHz, CDCl3) δ 14.1, 22.6, 23.1, 23.4, 25.8, 28.4, 29.3, 29.5, 31.8, 52.4, 56.6, 66.6, 88.7, 96.3, 113.5, 117.1, 118.3, 119.6, 120.3, 123.1, 123.7, 125.0, 125.3, 126.6, 126.9, 127.4, 127.5, 128.3, 128.9, 129.0, 129.3, 129.4, 129.8, 130.2, 130.4, 130.7, 131.4, 132.5, 136.6, 137.1, 141.3, 143.2, 159.1, 163.5, 167.7. Monomer, (P)-2 (n = 1) Under

an

argon

atmosphere,

a

solution

of

(P)-17

(314

mg,

0.40

mmol),

tris(dibenzylidenacetone)dipalladium(0) chloroform adduct (11.7 mg, 0.01 mmol), cuprous iodide (23.1

mg,

0.12

mmol),

tris(2,4,6-trimethylphenyl)phosphine

(23.3

mg,

0.06

mmol),

triphenylphosphine (15.9 mg, 0.06 mmol), tetrabutylammonium iodide (448 mg, 1.2 mmol) in trietylamine (0.3 mL), and N,N-dimethylformamide (4.3 mL) was freeze-evacuated three times. Then, trimethylsilylacetylene (119 mg, 1.2 mmol) was added, and the mixture was stirred for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene = 1:1 and 1:2) gave (P)-2 (n = 1) (269 mg, 0.36 mmol, 27 ACS Paragon Plus Environment


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Page 28 of 51

92%) as a yellow solid. Mp 60-61 °C (CH2Cl2-methanol). [α]27D −472 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C47H53O5Si+ ([M+H]+): 725.37. Found: 725.94. Anal. (C47H52O5Si) Calcd.: C, 77.86; H, 7.23. Found: C, 77.73; H, 7.39. IR (KBr) 2924, 2852, 2151, 1714, 1244, 841 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.30 (9H, s), 0.89 (3H, t, J = 7.0 Hz), 1.28-1.49 (14H, m), 1.83 (2H, quint, J = 7.2 Hz), 1.89 (3H, s), 1.93 (3H, s), 4.07 (3H, s), 4.08 (3H, s), 4.38 (2H, t, J = 7.2 Hz), 7.42 (1H, d, J = 6.8 Hz), 7.47 (1H, d, J = 7.2 Hz), 7.51 (1H, s), 7.65 (1H, dd J = 7.2, 8,4 Hz), 7.72 (1H, t, J = 7.4 Hz), 7.87 (1H, s), 8.13 (1H, s), 8.45 (1H, s), 8.62 (1H, d, J = 7.6 Hz), 8.82 (1H, d, J = 8.0 Hz).13C NMR (100 MHz, CDCl3) δ −0.025, 14.1, 22.6, 23.1, 23.4, 26.0, 28.6, 29.3, 29.5, 31.9, 52.4, 56.2, 65.8, 89.7, 94.4, 98.3, 102.7, 112.1, 115.7, 116.4, 120.2, 123.0, 123.9, 126.8, 127.3, 127.4, 128.9, 129.0, 129.3, 129.4, 129.9, 130.0, 130.1, 130.7, 131.4, 132.7, 133.3, 136.5, 137.0, 139.3, 159.4, 166.0, 167.8. Deprotected monomer, (P)-2-H (n = 1) Under an argon atmosphere, to a solution of (P)-2 (n = 1) (135 mg, 0.10 mmol) in tetrahydrofuran (7.5 mL) was added a tetrahydrofuran solution of tetrabutylammonium fluoride (0.15 mL, 0.15 mmol) at 0 °C, and the mixture was stirred at 0 °C for 10 min. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 5:1) gave (P)-2-H (n = 1) (126 mg, 0.099 mmol, 99%) as a yellow solid. Mp

51-52

°C

(CH2Cl2-methanol). [α]27D −449 (c 0.10, CHCl3). MALDI-TOF

MS

(α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C44H44NaO5+ ([M+Na]+): 675.31. Found: 674.58. Anal. (C44H44O5) Calcd.: C, 80.95; H, 6.79. Found: C, 81.01; H, 7.01. IR (KBr) 2923, 2852, 2203, 1714, 1241, 782 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.89 (3H, t, J = 7.0 Hz), 1.28-1.52 (14H, m), 1.82 (2H, quint, J = 7.1 Hz), 1.90 (3H, s), 1.94 (3H, s), 3.33 (1H, s), 4.08 (3H, s), 4.09 (3H, s), 4.39 (2H, t, J = 6.8 Hz), 7.44 (1H, d, J = 7.2 Hz), 7.48 (1H, d, J = 7.2 Hz), 7.54 (1H, s), 7.66 (1H, dd, J = 7.2, 8.4 Hz), 7.72, (1H, dd, J = 7.2, 8.0 Hz), 7.89 (1H, s), 8.16 (1H, s), 8.47 (1H, s), 8.61 (1H, d, J = 8.0 Hz), 8.81 (1H, d, J = 8.4 Hz). 13C NMR (100 MHz, CDCl3) δ 14.1, 22.7, 23.1, 23.4, 26.1, 28.6, 29.26, 29.29, 29.5, 31.9, 52.4, 56.3, 65.9, 81.0, 81.4, 89.6, 94.7, 112.2, 115.0, 116.7, 120.2, 123.1, 123.8, 126.8, 127.3, 127.4, 128.9, 129.1, 129.3, 129.4, 130.0, 130.09, 130.12, 130.7, 131.5, 132.7, 133.5, 136.6, 137.1, 139.4, 159.6, 165.7, 167.8. Dimer, (P)-2 (n = 2) Under an argon atmosphere, a mixture tetrakis(triphenylphosphine)dipalladium(0) (22.9 mg, 0.02 mmol),

cuprous

iodide

(5.7

mg,

0.03

mmol),

(P)-5


(83.4

mg,

0.01

mmol)

in

Page 29 of 51

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N,N-dimethylformamide (2.0 mL), tetrahydrofuran (2.0 mL), and triethylamine (0.25 ml) was freezed-evacuated three times. To the mixture, A solution of (P)-2-H (n = 1) (83.9 mg, 0.13 mmol) in N,N-dimethylformamide (0.5 mL) and tetrahydrofuran (0.5 mL) was added dropwise over 45 min, and the resulted mixture was stirred 45 °C for 3 h. The reaction was quenched by saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene= 1:1 to hexane:etylacetate= 8:1 to 6:1), and GPC (toluene) gave (P)-2 (n = 2) (118 mg, 0.88 mmol, 80 %) as a yellow solid. Mp 107-108 °C (CH2Cl2-methanol). [α]27D −308 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C90H93O9Si+ ([M+H]+): 1345.66. Found: 1346.12. Anal. (C90H92O9Si) Calcd.: C, 80.32; H, 6.89. Found: C, 80.13; H, 7.11. IR (KBr) 2923, 2852, 2199, 2152, 1719, 1239, 783 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.33 (9H, s), 0.86 (3H, t, J = 7.0 Hz), 0.88 (3H, t, J = 7.0 Hz), 1.16-1.50 (28H, m), 1.69 (3H, s), 1.74 (2H, quint, J = 7.3 Hz), 1.79 (3H, s), 1.80-1.85 (2H, m), 1.85 (3H, s), 1.87 (3H, s), 3.92 (3H, s), 4.04 (3H, s), 4.16 (3H, s), 4.33 (2H, t, J = 6.6 Hz), 4.38 (2H, t, J = 7.0 Hz), 7.22 (1H, d, J = 6.8 Hz), 7.30-7.44 (5H, m), 7.48 (1H, dd, J = 7.2, 8.4 Hz), 7.66 (1H, dd, J = 7.2, 8.4 Hz), 7.70 (1H, s), 7.84 (1H, s), 7.97 (1H, s), 8.12 (1H, s), 8.23 (2H, s), 8.25 (1H, s), 8.39 (1H, d, J = 7.6 Hz), 8.45 (1H, s), 8.55 (1H, d, J = 8.4 Hz), 8.70 (1H, d, J = 7.6 Hz), 8.80 (1H, d, J = 8.4 Hz). 13C NMR (100 MHz, CDCl3) δ −0.145, 14.1, 22.6, 22.9, 23.0, 23.3, 23.4, 26.0, 26.1, 28.7, 29.27, 29.29, 29.31, 29.49, 29.50, 29.52, 29.55, 31.9, 52.1, 52.3, 56.4, 65.8, 66.0, 89.5, 91.2, 92.5, 94.4, 94.7, 95.1, 102.3, 102.5, 112.6, 115.5, 117.0, 119.91, 119.95, 122.8, 122.9, 123.0, 123.6, 123.8, 125.4, 126.55, 126.61, 127.1, 127.3, 127.6, 128.6, 128.8. 128.86, 128.90, 129.1, 129.2, 129.3, 129.4, 129.5, 129.7, 129.82, 129.84, 130.0, 130.1, 130.5, 130.6, 130.7, 131.2, 131.4, 131.6, 132.4, 132.5, 132.9, 134.0, 136.3, 136.5, 136.88, 136.94, 138.1, 139.1, 159.8, 165.1, 165.7, 167.4, 167.7. Deprotected dimer, (P)-2-H (n = 2) Under an argon atmosphere, to a solution of (P)-2 (n = 2) (118 mg, 0.88 mmol) in tetrahydrofuran (6.5 mL) was added a tetrahydrofuran solution of tetrabutylammonium fluoride (0.13 mL, 0.13 mmol) at 0 °C, and the mixture was stirred at 0 °C for 10 min. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 5:1) gave (P)-2-H (n = 2) (110.9 mg, 0.87 mmol, 99 %) as a yellow solid. Mp 101-102 °C (CH2Cl2-methanol). [α]27D −321 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C87H84O9 (M+): 1272.61. Found: 1273.08. Anal. 29 ACS Paragon Plus Environment


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(C87H84O9) Calcd.: C, 82.05; H, 6.65. Found: C, 81.81; H, 6.96. IR (KBr) 2925, 2853, 2202, 1717, 1241, 783 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.86 (3H, t, J = 7.0 Hz), 0.88 (3H, t, J = 7.0 Hz), 1.16-1.53 (28H, m), 1.69 (3H, s), 1.75 (2H, quint, J = 7.3 Hz), 1.79 (3H, s), 1.81-1.83 (2H, m), 1.85 (3H, s), 1.87 (3H, s), 3.56 (1H, s), 3.91 (3H, s), 4.04 (3H, s), 4.16 (3H, s), 4.34 (2H, t, J = 6.6 Hz), 4.40 (2H, t, J = 6.6 Hz), 7.22 (1H, d, J = 7.2 Hz), 7.30-7.44 (5H, m), 7.48 (1H, dd, J = 7.2, 8.0 Hz), 7.66 (1H, dd, J = 7.2, 8.4 Hz), 7.70 (1H, s), 7.83 (1H, s), 8.01 (1H, s), 8.13 (1H, s), 8,22 (1H, s), 8.25 (1H, s), 8.27 (1H, s), 8.40 (1H, d, J = 7.6 Hz), 8.45 (1H, s), 8.54 (1H, d, J = 8.4 Hz), 8.68 (1H, d, J = 8.0 Hz), 8.81 (1H, d, J = 8.4 Hz).

13

C NMR (100 MHz, CDCl3) δ 14.1, 22.66, 22.67, 23.0,

23.1, 23.36, 23.42, 26.05, 26.12, 28.6, 28.7, 29.30, 29.32, 29.51, 29.54, 29.55, 29.58, 31.9, 52.2, 52.3, 56.4, 65.9, 66.1, 81.3, 84.3, 89.5, 91.1, 92.3, 94.5, 95.0, 95.1, 112.7, 115.5, 117.0, 119.8, 120.0, 122.2, 122.8, 123.0, 123.6, 123.7, 125.9, 126.6, 126.7, 127.2, 127.3, 127.7, 128.8, 128.9, 129.0, 129.1, 129.3, 129.4, 129.49, 129.52, 129.7, 129.9, 130.07, 130.12, 130.6, 130.7, 130.8, 131.2, 131.4, 131.7, 132.4, 132.5, 133.0, 134.1, 136.4, 136.5, 136.9, 137.0, 138.3, 139.1, 159.9, 164.9, 165.7, 167.5, 167.8. Trimer, (P)-2 (n = 3) Under

an

argon

atmosphere,

a

solution

of

(P)-5

(150

mg,

2.2

mmol),


mg,

0.32

mmol),


(63.4

mg,

0.16

mmol),

triphenylphosphine (42.9 mg, 0.16 mmol), and tetrabutylammonium iodide (760 mg, 2.0 mmol) in trietylamine (0.34 mL), N,N-dimethylformamide (2.4 mL), and tetrahydrofuran (2.4 mL) was freeze-evacuated three times. A solution of (P)-2-H (n = 2) (90.1 mg, 0.071 mmol) in N,N-dimethylformamide (1.0 mL) and tetrahydrofuran (1.0 mL) was freeze-evacuated three times, and was added to the above mixture dropwise. The resulted mixture was stirred at 45 °C for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene = 1:1, 1:2, hexane:ethyl acetate = 8:1, 4:1, hexane:toluene:ethyl acetate =2:2:1), and GPC (toluene) gave (P)-2 (n = 3) (101 mg, 0.052 mmol, 73 %) as a yellow solid. Mp 122-124 °C (CHCl3-methanol). [α]27D −171 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C133H132O13Si (M+): 1964.94. Found: 1965.35. Anal. (C133H132O13Si) Calcd.: C, 81.23; H, 6.77. Found: C, 81.36; H, 7.02. IR (KBr) 2925, 2853, 2360, 1716, 1541, 1507, 1240 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.35 (9H, s), 0.81 (3H, t, J = 7.0 Hz), 0.86 (3H, t, J = 6.8 Hz), 0.90 (3H, t, J = 6.8 Hz), 1.17-1.53 (42H, m), 1.59 (3H, s), 1.68 (3H, s), 1.74 (3H, s), 1.76-1.90 (6H, m), 1.81 (3H, s), 1.87 (6H, s), 3.83 (3H, s), 3.91 (3H, 30 ACS Paragon Plus Environment

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s), 4.03 (3H, s), 4.19 (3H, s), 4.35-4.43 (6H, m), 7.09-7.14 (2H, m), 7.19 (2H, dd, J = 7.2, 8.4 Hz), 7.25 (2H, d, J = 8.0 Hz), 7.30 (2H, dd, J = 7.2, 8.4 Hz), 7.38 (1H, d, J = 6.8 Hz), 7.41-7.45 (2H, m), 7.57 (1H, dd, J = 7.2, 8.0 Hz), 7.66 (1H, dd, J = 7.0, 8.2 Hz), 7.74 (1H, s), 7.80 (1H, s), 7.88 (1H, s), 8.01 (1H, s), 8.13 (1H, s), 8.187 (1H, s), 8.191 (1H, s), 8.26 (1H, s), 8.299 (1H, s), 8.301 (1H, s), 8.42-8.45 (3H, m), 8.47-8.50 (3H, m), 8.72 (1H, d, J = 8.0 Hz), 8.81 (1H, d, J = 8.0 Hz). 13C NMR (100 MHz, CDCl3) δ −0.15, 14.07, 14.10, 22.63, 22.66, 22.9, 22.96, 23.05, 23.3, 23.35,

23.40,

26.0, 26.08, 26.14, 28.68, 28.72, 29.3, 29.53, 29.55, 29.57, 31.9, 52.1, 52.2, 52.3, 56.4, 65.8, 66.0, 66.1, 89.5, 91.4, 92.3, 92.4, 94.1, 94.5, 94.8, 95.0, 95.26, 95.30,102.4, 102.7, 122.7, 115.5, 117.1, 119.6, 119.87, 119.95, 122.68, 122.73, 122.8, 123.0, 123.4, 123.5, 123.6, 123.7, 124.9, 125.8, 126.3, 126.6, 127.1, 127.2, 127.3, 127.7, 128.78, 128.84, 128.89, 128.94, 129.1, 129.2, 129.29, 129.35, 129.38, 129.51, 129.53, 129.6, 129.7, 129.9, 130.04, 130.05, 130.1, 130.5, 130.6, 130.7, 130.8, 131.12, 131.15, 131.4, 131.8, 132.2, 132.4, 132.5, 133.0, 134.3, 134.6, 136.31, 136.33, 136.5, 136.8, 136.9, 137.1, 138.0, 138.2, 139.1, 159.9, 164.9, 165.1, 165.7, 167.32, 167.34, 167.7. Deprotected trimer, (P)-2-H (n = 3) Under an argon atmosphere, to a solution of (P)-2 (n = 3) (101 mg, 0.052 mmol) in tetrahydrofuran (8.0 mL) was added a tetrahydrofuran solution of tetrabutylammonium fluoride (0.08 mL, 0.08 mmol) at 0 °C, and the mixture was stirred at 0 °C for 10 min. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene:ethyl acetate = 4:4:1) gave (P)-2-H (n = 3) (97.5 mg, 0.051 mmol, 99%) as a yellow solid. Mp 114-115 °C (CH2Cl2-methanol). [α]27D −181 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C130H125O13+ ([M+H]+): 1893.91. Found: 1895.46. Anal. (C130H124O13) Calcd.: C, 82.42; H, 6.60. Found: C, 81.93; H, 6.94. IR (KBr) 2925, 2359, 1716, 1541, 1507, 1240 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.81 (3H, t, J = 7.0 Hz), 0.84-0.90 (6H, m), 1.17-1.54 (42H, m), 1.59 (3H, s), 1.68 (3H, s), 1.74 (3H, s), 1.74-1.87 (6H, m), 1.81 (3H, s), 1.87 (3H, s), 3.59 (1H, s), 3.83 (3H, s), 3.90 (3H, s), 4.03 (3H, s), 4.19 (3H, s), 4.34-4.43 (6H, m), 7.09-7.14 (2H, m), 7.18-7.32 (5H, m), 7.38 (1H, d, J = 6.8 Hz), 7.41-7.45 (2H, m), 7.56 (1H, dd, J = 7.2, 8.4 Hz), 7.66 (1H, dd, J = 7.2, 8.4 Hz), 7.73 (1H, s), 7.82 (1H, s), 7.88 (1H, s), 8.04 (1H, s), 8.13 (1H, s), 8.19 (1H, s), 8.20 (1H, s), 8.26 (1H, d, J = 0.4 Hz), 8.31 (1H, s), 8.33 (1H, d, J = 0.8 Hz), 8.24-8.50 (6H, m), 8.70 (1H, d, J = 7.6 Hz), 8.81 (1H, d, J = 8.0 Hz).

13

C NMR (100 MHz,

CDCl3) δ 14.07, 14.10, 22.6, 22.66, 22.67, 22.9, 23.0, 23.1, 23.3, 23.36, 23.41, 26.05, 26.10, 26.14, 28.6, 28.7, 29.3, 29.5, 29.6, 31.9, 52.1, 52.2, 52.3, 56.4, 66.0, 66.1, 81.3, 84.6, 89.4, 91.4, 92.25, 92.27, 94.25, 94.27, 94.9, 95.27, 95.29, 95.4, 112.7, 115.5, 117.1, 119.6, 119.8, 119.9, 122.70, 31 ACS Paragon Plus Environment


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Page 32 of 51

122.71, 123.0, 123.5, 123.6, 123.7, 125.4, 125.9, 126.4, 126.6, 127.1, 127.2, 127.3, 127.7, 128.78, 128.80, 128.9, 129.0, 129.15, 129.18, 129.3, 129.4, 129.5, 129.6, 129.7, 129.8, 129.9, 130.05, 130.08, 130.14, 130.5, 130.6, 130.7, 130.9, 131.1, 131.2, 131.4, 131.8, 132.2, 132.4, 132.5, 133.0, 134.3, 134.6, 136.33, 136.35, 136.5, 136.8, 137.0, 137.1, 138.0, 138.3, 139.1, 159.9, 164.9, 165.7, 167.3, 167.7. Tetramer, (P)-2 (n = 4) Under

an

argon

atmosphere,

a

solution

of

(P)-5

(128

mg,

0.15

mmol),


mg,

0.23

mmol),


(45.0

mg,

0.12

mmol),

triphenylphosphine (30.0 mg, 0.12 mmol), and tetrabutylammonium iodide (536 mg, 1.45 mmol) in trietylamine (0.33 mL), N,N-dimethylformamide (2.3 mL), and tetrahydrofuran (2.3 mL) was freeze-evacuated three times. A solution of (P)-2-H (n = 3) (96.0 mg, 0.05 mmol) in N,N-dimethylformamide (1.0 mL), and tetrahydrofuran (1.0 mL) was freeze-evacuated three times, and was added dropwise to the above mixture. The resulted mixture was stirred at 45 °C for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene = 1:1, 1:2, hexane:toluene:ethyl acetate =2:2:1), and GPC (toluene) gave (P)-2 (n = 4) (93.1 g, 0.036 mmol, 72 %) as a yellow solid. Mp 143-144 °C (CH2Cl2-methanol). [α]27D −100 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C176H173O17Si+ ([M+H]+): 2586.24. Found: 2587.16. Anal. (C176H172O17Si) Calcd.: C, 81.70; H, 6.70. Found: C, 81.67; H, 6.80. IR (KBr) 2925, 2853, 2321, 1716, 1521, 1507, 1239 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.34 (9H, s), 0.80-0.90 (12H, m), 1.18-1.51 (56H, m), 1.57 (3H, s),1.59 (3H, s), 1.67 (3H, s), 1.75 (6H, s), 1.81 (3H, s), 1.87 (6H, s), 1.75-1.87 (8H, m), 3.83 (3H, s), 3.84 (3H, s), 3.94 (3H, s), 4.04 (3H, s), 4.19 (3H, s), 4.34-4.42 (8H, m), 7.08-7.34 (11H, m), 7.38-7.45 (3H, m), 7.55 (1H, dd, J = 7.6, 8.0 Hz), 7.66 (1H, dd, J = 7.2, 8.4 Hz), 7.74 (1H, s), 7.84 (1H, s), 7.88 (1H, s), 7.98 (1H, s), 8.00 (1H, d, J = 0.04 Hz), 8.12 (1H, s), 8.19 (1H, s), 8.20 (1H, s), 8.22 (1H, s), 8.27 (1H, s), 8.30 (2H, s), 8.32 (1H, s), 8.39-8.51 (9H, m), 8.71 (1H, d, J = 8.0 Hz), 8.80 (1H, d, J = 8.4 Hz).

13

C NMR (100 MHz, CDCl3) δ −0.14, 14.07, 14.10, 33.64, 22.66,

22.86, 22.95, 23.04, 23.3, 23.35, 23.41, 25.99, 26.09, 26.12, 26.14, 28.69, 28.73, 28.8, 29.3, 29.5, 29.6, 31.9, 52.07. 52.12, 52.26, 52.31, 56.4, 65.9, 66.0, 66.1, 89.5, 91.4, 92.21, 92.25, 92.4, 94.1, 94.5, 94.6, 94.8, 94.9, 95.0, 95.3, 95.5, 95.6, 102.4, 102.8, 112.7, 115.6, 117.1, 119.58, 119.63, 119.9, 120.0, 122.6, 122.7, 122.8, 123.0, 123.3, 123.4, 123.5, 123.6, 123.7, 124.9, 125.3, 126.0, 126.3, 126.4, 126.7, 127.08, 127.14, 127.2, 127.3, 127.4, 127.7, 128.8, 128.86, 128.90, 129.0, 129.1, 32 ACS Paragon Plus Environment

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129.20, 129.23, 129.31, 129.35, 129.50, 129.56, 129.59, 129.7, 129.9, 130.1, 130.2, 130.48, 130.52, 130.6, 130.7, 130.8, 131.07, 131.14, 131.2, 131.3, 131.4, 131.8, 132.2, 132.3, 132.4, 132.5, 133.0, 134.3, 134.7, 134.9, 136.30, 136.35, 136.53, 136.8, 136.9, 137.0, 137.1, 138.0, 138.2, 139.1, 159.9, 164.88, 164.89, 165.1, 165.6, 167.2, 167.35, 167.37, 167.7. Deprotected tetramer, (P)-2-H (n = 4) Under an argon atmosphere, to a solution of (P)-2 (n = 4) (69.8 mg, 0.027 mmol) in tetrahydrofuran (4.1 mL) was added a tetrahydrofuran solution of tetrabutylammonium fluoride (0.04 ml, 0.04 mmol) at 0 °C, and the mixture was stirred at 0 °C for 10 min. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene:ethyl acetate = 2:2:1) gave (P)-2-H (n = 4) (62.9 mg, 0.025 mmol, 92 %) as a yellow solid. Mp 134-135 °C (CH2Cl2-methanol). [α]27D −59 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C173H165O17+ ([M+H]+): 2514.20. Found: 2516.92. Anal. (C173H164O17) Calcd.: C, 82.61; H, 6.57. Found: C, 82.16; H, 7.09. IR (KBr) 2924, 2852, 1716, 1541, 1507, 1457, 1238 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.80-0.90 (12H, m), 1.18-1.53 (56H, m), 1.57 (3H, s),1.59 (3H, s), 1.68 (3H, s), 1.75 (6H, s), 1.82 (3H, s), 1.87 (6H, s), 1.75-1.87 (8H, m), 3.59 (1H, s), 3.83 (3H, s), 3.84 (3H, s), 3.94 (3H, s), 4.04 (3H, s), 4.19 (3H, s), 4.35-4.43 (8H, m), 7.08-7.34 (11H, m), 7.38-7.45 (3H, m), 7.55 (1H, dd, J = 7.2, 8.0 Hz), 7.66 (1H, dd, J = 7.2, 8.4 Hz), 7.74 (1H, s), 7.84 (1H, s), 7.89 (1H, s), 7.98 (1H, s), 8.05 (1H, s), 8.12 (1H, s), 8.19 (1H, s), 8.20 (1H, s), 8.22 (1H, s), 8.28 (1H, s), 8.30 (1H, s), 8.33 (1H, s), 8.34 (1H, s), 8.45 (1H, s), 8.47 (1H, s), 8.50 (1H, s), 8.39-8.50 (6H, m), 8.70 (1H, d, J = 8.4 Hz), 8.80 (1H, d, J = 8.8 Hz).

13

C

NMR (100 MHz, CDCl3) δ 14.08, 14.11, 22.6, 22.9, 23.0, 23.1, 23.3, 23.36, 23.42, 26.06, 26.10, 26.12, 26.14, 28.6, 28.7, 28.8, 29.3, 29.56, 29.58, 31.9, 52.09, 52.14, 52.28, 52.33, 56.4, 66.0, 66.1, 81.3, 84.6, 89.5, 91.4, 92.17, 92.23, 94.2, 94.5, 94.9, 95.28, 95.33, 95.5, 95.6, 112.7, 115.5, 117.1, 119.5, 119.6, 119.8, 119.9, 122.6, 122.8, 123.0, 123.2, 123.4, 123.5, 123.6, 123.7, 125.3, 125.4, 126.0, 126.3, 126.4, 126.7, 127.2, 127.3, 127.7, 128.77, 128.81, 128.9, 129.0, 129.1, 129.2, 129.3, 129.5, 129.6, 129.8, 129.85, 129.89, 130.06, 130.10, 130.15, 130.48, 130.52, 130.6, 130.7, 130.9, 131.07, 131.14, 131.2, 131.3, 131.4, 131.9, 132.21, 132.25, 132.4, 132.5, 133.0, 134.4, 134.7, 134.9, 136.3, 136.4, 136.5, 136.86, 136.91, 137.0, 137.1, 138.1, 138.4, 139.1, 159.9, 164.87, 164.90, 165.6, 167.2, 167.4, 167.7. Decyl 2-hydroxy-4-iodo-5-tetrahydropyranyloxybenzoate, 18 Under an argon atmosphere, a solution of 8 (56.1 mg, 0.13 mmol), pyridinium p-toluenesulfonate (6 33 ACS Paragon Plus Environment


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mg, 0.024 mmol) and dihydropyran (0.037 mL, 0.4 mmol) in dichloromethane (4.0 mL) was stirred at room temperature for 10 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 30: 1, 20:1) gave 17 (67.7 mg, 0.13 mmol, 79 %) as a colorless oil. LRMS (EI) m/z 504.1 (M+, 0.13%), 420.0 ([M−C5H8O]+, 100%), 279.9 ([M−C5H8O−C10H20]+, 94%), 261.9 ([M−C5H9O−C10H21]+, 72%), 84.5 (C5H8O, 28%). HRMS (EI) m/z Calcd. for C22H33IO5 (M+): 504.1373. Found: 504.1390. IR (KBr) 3186, 2925, 2854, 1675, 1467, 1204, 1095 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.88 (3H, t, J = 6.8 Hz), 1.27-1.43 (14H, m), 1.62-1.77 (3H, m), 1.77 (2H, quint, J = 7.2 Hz), 1.84-1.92 (1H, m), 1.97-2.01 (1H, m), 2.07-2.17 (1H, m), 3.59-3.63 (1H, m), 3.89 (1H, dt, J = 2.8, 11.0 Hz), 4.27-4.37 (2H, m), 5.41 (1H, t, J = 2.8 Hz), 7.47 (2H, d, J = 8.0 Hz), 10.48 (1H, s).

13

C NMR (100 MHz,

CDCl3) δ 14.1, 18.3, 22.7, 25.2, 25.8, 28.5, 29.2, 29.3, 29.5, 30.1, 31.8, 61.8, 65.7, 97.4, 97.7,122.6, 114.7, 128.1, 148.2, 156.4, 168.7. Decyl 4-iodo-5-tetrahydropyranyloxy-2-trifluoromethanesulfonyloxybenzoate, 19 Under an argon atmosphere, to a solution of 17 (34.4 mg, 0.067 mmol) in dichloromethane (2.0 mL) was added triethylamine (0.08 mL) and trifluoromethanesulfonic anhydride (77.6mg, 0.28 mmol) at −100 °C, and the mixture was stirred at 0 °C for 2 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 12:1) gave 18 (33.2 mg, 0.052 mmol, 77 %) as a colorless oil. MS (FAB, NBA) m/z Calcd. for C23H33F3IO7S ([M+H]+): 637.0944. Found: 637.0941. IR (KBr) 2927, 2855, 1734, 1429, 1208, 907 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.88 (3H, t, J = 6.8 Hz), 1.26-1.41 (14H, m), 1.63-1.81 (5H, m), 1.85-1.93 (1H, m), 1.98-2.02 (1H, m), 2.06-2.17 (1H, m), 3.63-3.67 (1H, m), 3.78 (1H, dt, J = 2.9, 11.3 Hz), 4.30-4.40 (2H, m), 5.61 (1H, t, J = 2.6 Hz), 7.67 (2H, s).

13

C NMR (100 MHz,

CDCl3) δ 14.0, 18.0, 22.6, 24.9, 25.7, 28.3, 29.1, 29.2, 29.4, 29.8, 31.8, 61.8, 66.3, 92.1, 97.1, 116.4, 118.6 (q, JC-F = 319.5 Hz), 125.4, 132.9, 141.5, 155.3, 163.3. Decyl 3-iodobenzoate, 20 Under an argon atmosphere, a solution of 3-iodobenzoic acid (1.24 g, 5.0 mmol), and potassium carbonate (1.38 g, 10.0 mmol) in N,N-dimethylformamide (10 mL) was added 1-bromodecane (1.22 g, 5.5 mmol) at room temperature, and the mixture was stirred at 60 °C for 2 h. The reaction was quenched by adding water, and the organic materials were extracted with ethyl acetate. The organic 34 ACS Paragon Plus Environment

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layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane only, hexane:ethyl acetate = 30:1) gave 19 (1.9 g, 5.0 mmol, 100%) as a colorless oil. LRMS (EI) m/z 388.1 (M+, 13%), 247.9 ([M−C10H20]+, 100%). HRMS (EI) m/z Calcd. for C17H25IO2 (M+): 388.0899. Found: 388.0892. IR (KBr) 2925, 2854, 1724, 1566, 1467, 1256, 1118, 744 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.88 (3H, t, J = 6.8 Hz), 1.27-1.46 (14H, m), 1.76 (2H, quint, J = 7.1 Hz), 4.31 (2H, t, J = 6.8 Hz), 7.18 (1H, t, J = 8.2 Hz), 7.88 (1H, ddd, J = 1.1, 1.9,8.1 Hz), 8.00 (1H, ddd, J = 0.8, 1.6, 8.0 Hz), 8.37 (1H, t, J = 1.6 Hz). 13C NMR (100 MHz, CDCl3) δ 14.1, 22.6, 25.9, 28.6, 29.20, 29.25, 29.46, 29.48, 31.8, 65.5, 93.7, 128.6, 129.9, 132.3, 138.3, 141.5, 165.1. Precursor of the monomer (P)-2-OTHP, (P)-21 Under

an

argon

atmosphere,

a

solution

of

19

(300

mg,

0.47

mmol),

tris(dibenzylidenacetone)dipalladium(0) chloroform adduct (11,3 mg, 0.01 mmol), cuprous iodide (22.3

mg,

0.12

tetrabutylammonium

mmol), iodide

tris(2,4,6-trimethylphenyl)phosphine (432

mg,

1.17

mmol)

in

(22.7

mg,

trietylamine

0.06

(0.3

mmol),

mL),

and

N,N-dimethylformamide (5 mL) was freeze-evacuated three times. A solution of (P)-15 (152 mg, 0.39 mmol) in N,N-dimethylformamide (2.0 mL) was freeze-evacuated three times, and was added to the above mixture. The mixture was stirred at room temperature for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate =20:1, 10:1) gave (P)-21 (343 g, 0.39 mmol, 100 %) as a yellow oil. [α]27D −328 (c 0.10, CHCl3). MS (FAB, NBA) m/z Calcd. for C47H49F3O9S (M+): 846.3049. Found: 846.3011. Anal. (C47H49F3O9S) Calcd: C, 66.65; H, 5.83. Found: C, 66.42; H, 5.81. IR (KBr) 2926, 2854, 2206, 1718, 1427, 1247, 1207 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.89 (3H, t, J = 6.8 Hz), 1.28-1.46 (14H, m), 1.64-1.69 (1H, m), 1.74-1.84 (2H, m), 1.81 (2H, quint, J = 7.0 Hz), 1.91 (3H, s), 1.95 (3H, s), 2.00-2.10 (1H, m), 2.18-2.35 (2H, m), 3.72-3.75 (1H, m), 3.95-4.00 (1H, m), 4.09 (3H, s), 4.37-4.43 (2H, m), 5.73 (1H, t, J = 2.8 Hz), 7.45 (1H, d, J = 7.2 Hz), 7.49 (1H, dd, J = 0.8, 7.2 Hz), 7.51 (1H, s), 7.65-7.69 (2H, m), 7.93 (1H, s), 8.16 (1H, s), 8.47 (1H, s), 8.64 (1H, d, J = 8.0 Hz), 8.82 (1H, d, J = 8.4 Hz). 13C NMR (100 MHz, CDCl3) δ 14.1, 18.4, 22.7, 23.1, 23.4, 25.0, 25.8, 28.4, 29.2, 29.3, 29.5, 30.1, 31.9, 52.4, 62.0, 66.4, 89.0, 89.1, 95.76, 95.79, 97.17, 97.20, 117.8, 117.9, 118.7 (q, JC-F = 319.5 Hz), 118.9, 119.0, 119.8, 123.1, 123.6, 123.7, 125.0, 126.4, 127.0, 127.20, 127.25, 27.5, 129.0, 129.2, 129.3, 129.4, 129.9, 130.2, 130.4, 130.8, 131.4, 132.50, 132.52, 136.6, 137.2, 141.8, 156.7, 156.8, 163.4, 167.8.



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Monomer, (P)-2-OTHP (n = 1) Under

an

argon

atmosphere,

a

solution

of

(P)-21

(343

mg,

0.39

mmol),


mg,

0.12

mmol),


(22.9

mg,

0.06

mmol),

triphenylphosphine (15.2 mg, 0.06 mmol), tetrabutylammonium iodide (432 mg, 1.17 mmol) in trietylamine (0.3 mL), and N,N-dimethylformamide (6.0 mL) was freeze-evacuated three times. Then, trimethylsilylacetylene (0.17 mL, 1.17 mmol) was added, and the mixture was stirred for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 20:1, 10:1) gave (P)-2-OTHP (n = 1) (248.1 g, 0.31 mmol, 80%) as a yellow solid. Mp 67-68 °C (CH2Cl2-methanol). [α]27D −395 (c 0.10, CHCl3). MS (FAB, NBA) m/z Calcd. for C51H59O6Si+ ([M+H]+): 795.4081. Found: 795.4064. Anal. (C51H58O6Si) Calcd.: C, 77.04; H, 7.35. Found: C, 77.03; H, 7.40. IR (KBr) 2925, 2853, 2153, 1717, 1244 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.29 (9H, s), 0.89 (3H, t, J = 7.0 Hz), 1.24-1.53 (14H, m), 1.65-1.68 (1H, m), 1.73-1.84 (4H, m), 1.91 (3H, s), 1.95 (3H, s), 1.99-2.12 (1H, m), 2.16-2.32 (2H, m), 3.70 (1H, dt, J = 4.0, 11.2 Hz), 3.99 (1H, dt, J = 2.8, 11.0 Hz), 4.10 (3H, s), 4.33-4.37 (2H, m), 5.73 (1H, t, J = 3.0 Hz), 7.44 (1H, d, J = 7.6 Hz), 7.48 (1H, d, J = 7.6 Hz), 7.64-7.70 (2H, m), 7.78 (1H, s), 7.87 (1H, s), 8.12 (1H, s), 8.46 (1H, s), 8.67 (1H, d, J = 8.0 Hz), 8.81 (1H, d, J = 8.0 Hz).13C NMR (100 MHz, CDCl3). δ −0.018, 14.1, 18.5, 22.7, 23.1, 23.4, 25.1, 26.0, 28.6, 29.3, 29.5, 30.2, 31.9, 52.4, 62.0, 65.7, 90.03, 90.05, 93.94, 94.0, 96.77, 96.79, 98.2, 102.7, 116.28, 116.31, 116.32, 117.0, 117.1, 120.5, 123.1, 123.87, 123.91, 126.9, 127.1, 127.2, 127.3, 129.0, 129.3, 129.4, 129.9, 130.0, 130.1, 130.8, 131.5, 132.6, 133.5, 136.5, 137.1, 139.16, 139.18, 156.9, 157.0, 165.9, 167.9. Deprotected monomer, (P)-2-H-OTHP (n = 1) Under an argon atmosphere, to a solution of (P)-2-OTHP (n = 1) (127 mg, 0.16 mmol) in tetrahydrofuran (6.0 mL) was added a tetrahydrofuran solution of tetrabutylammonium fluoride (0.24 mL, 0.24 mmol) at 0 °C, and the mixture was stirred at 0 °C for 10 min. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 10:1) gave (P)-2-H-OTHP (n = 1) (117 mg, 0.16 mmol, 99%) as a yellow solid. Mp 64-65 °C (CH2Cl2-methanol). [α]27D −330 (c 0.10, CHCl3). Anal. (C48H50O6) Calcd.: C, 79.75; H, 6.97. Found: C, 79.75; H, 6.97. IR (KBr) 2925, 2851, 1716, 1242 36 ACS Paragon Plus Environment

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cm−1. 1H NMR (400 MHz, CDCl3) δ 0.89 (3H, t, J = 7.0 Hz), 1.28-1.50 (14H, m), 1.66-1.69 (1H, m), 1.73-1.86 (4H, m), 1.91 (3H, s), 1.95 (3H, s), 1.99-2.07 (1H, m), 2.17-2.33 (2H, m), 3.33 (1H, s), 3.71 (1H, dt, J = 3.6, 10.8 Hz), 3.99 (1H, dt, J = 2.8, 11.1 Hz), 4.09 (3H, s), 4.36 (2H, t, J = 6.8 Hz), 5.74 (1H, t, J = 2.8 Hz), 7.44 (1H, d, J = 7.2 Hz), 7.48 (1H, d, J = 7.2 Hz), 7.64-7.69 (2H, m), 7.82 (1H, s), 7.90 (1H, s), 8.13 (1H, s), 8.46 (1H, s), 8.66 (1H, d, J = 8.0 Hz), 8.81 (1H, d, J = 8.0 Hz). 13C NMR (100 MHz, CDCl3) δ 14.1, 18.5, 22.7, 23.1, 23.4, 25.1, 26.0, 28.6, 29.27, 29.32, 29.5, 29.6, 30.2, 31.9, 52.4, 62.0, 65.8, 81.0, 81.5, 89.88, 89.90, 94.19, 94.20, 96.80, 96.83, 115.6, 116.47, 116.50, 117.36, 117.37, 120.4, 123.1, 123.85, 123.88, 127.0, 127.18, 127.21, 127.4, 128.97, 129.017, 129.019, 129.3, 129.4, 130.01, 130.04, 130.1, 130.8, 131.5, 132.7, 133.6, 136.6, 137.2, 139.2, 139.3, 157.19, 157.22, 165.6, 167.9. Dimer, (P)-2-OTHP (n = 2) Under an argon atmosphere, a mixture tetrakis(triphenylphosphine)dipalladium(0) (27.7 mg, 0.024 mmol), cuprous iodide (6.9 mg, 0.036 mmol), and 15 (105 mg, 0.12 mmol) in N,N-dimethylformamide (2.2 mL), tetrahydrofuran (2.2 mL), and triethylamine (0.32 mL) was freezed-evacuated three times. To the mixture, a solution of (P)-2-H-OTHP (n = 1) (115 mg, 0.16 mmol) in N,N-dimethylformamide (1.0 mL) and tetrahydrofuran (1.0 mL) was added dropwise over 45 min, and the mixture was stirred 45 °C for 4 h. The reaction was quenched by saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene= 1:1 to hexane:etylacetate= 8:1 to 6:1), and GPC (toluene) gave (P)-2 -OTHP (n = 2) (165 mg, 0.12 mmol, 97%) as a yellow solid. Mp 100-101 °C (CH2Cl2-methanol). [α]27D −296 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C94H99O10Si+ ([M+H]+): 1415.70. Found: 1416.42. Anal. (C94H98O10Si) Calcd.: C, 79.74; H, 6.98. Found: C, 79.72; H, 6.96. IR (KBr) 2925, 2852, 2201, 2152, 1716, 1240 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.34 (9H, s), 0.84-0.90 (6H, m), 1.18-1.51 (28H, m), 1.69-1.77 (6H, m), 1.78-1.86 (7H, m), 1.88 (6H, s), 2.04-2.13 (1H, m), 2.23-2.38 (2H, m), 3.75-3.79 (1H, m), 3.88-3.89 (3H, s × 2: mixture of isomers), 4.02-4.03 (3H, s × 2: mixture of isomers), 4.04-4.10 (1H, m), 4.32 (2H, t, J = 6.8 Hz), 4.38 (2H, t, J = 7.0 Hz), 5.81-5.83 (1H, dt × 2: mixture of isomers, J = 2.8 Hz), 7.19-7.23 (1H, m), 7.28-7.37 (3H, m), 7.41-7.45 (2H, m), 7.50-7.54 (1H, m), 7.67 (1H, t, J = 7.8 Hz), 7.73-7.74 (1H, s × 2: mixture of isomers), 7.97-7.98 (2H, s × 3: mixture of isomers), 8.14-8.15 (2H, s × 3: mixture of isomers), 8.24 (1H, s), 8.28 (1H, s), 8.47-8.48 (1H, s × 2: mixture of isomers), 8.49-8.52 (2H, m), 8.70 (1H, d, J = 8.0 Hz), 8.80 (1H, d, J = 8.8 Hz).

13

C NMR (100 MHz, CDCl3) δ −0.15, 14.1, 18.5, 18.6, 22.6,

22.96, 23.02, 23.3, 23.4, 25.1, 25.96, 26.05, 28.6, 29.27, 29.29, 29.49, 29.54, 30.2, 31.8, 52.05, 37 ACS Paragon Plus Environment


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52.08, 52.2, 52.3, 62.0, 62.1, 65.7, 65.8, 89.76, 89.83, 91.2, 92.5, 94.41, 94.43, 94.55, 94.61, 94.63, 96.8, 96.9, 102.2, 102.5, 116.1, 116.8, 116.9, 117.5, 117.6, 119.9, 120.1, 122.70, 122.73, 122.8, 122.9, 123.0, 123.7, 123.8, 125.4, 126.5, 126.6, 126.8, 126.9, 127.0, 127.3, 127.6, 128.1, 128.60, 128.62, 128.77, 128.80, 128.81, 128.87, 128.94, 129.1, 129.15, 129.23, 129.4, 129.5, 129.7, 129.8, 130.0, 130.1, 130.56, 130.63, 130.7, 131.1, 131.4, 131.7, 132.4, 132.9, 134.1, 136.3, 136.4, 136.90, 136.93, 138.10, 138.11, 138.8, 138.9, 157.3, 157.4, 165.1, 165.51, 165.52, 167.3, 167.4, 167.58, 167.62. Deprotected dimer, (P)-2-H-OTHP (n = 2) Under an argon atmosphere, to a solution of (P)-2-OTHP (n = 2) (166 mg, 0.12 mmol) in tetrahydrofuran (8.0 mL) was added a tetrahydrofuran solution of tetrabutylammonium fluoride (0.18 mL, 0.18 mmol) at 0 °C, and the mixture was stirred at 0 °C for 10 min. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:ethyl acetate = 10:1, 8:1, 4:1) gave (P)-2-H-OTHP (n = 2) (149 mg, 0.11 mmol, 99%) as a yellow solid. Mp 98-99 °C (CH2Cl2-methanol). [α]27D −293 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C91H91NaO10+ ([M+Na+H]+): 1366.65. Found: 1366.37. Anal. (C91H90O10) Calcd.: C, 81.34; H, 6.75. Found: C, 81.42; H, 6.92. IR (KBr) 2925, 2852, 2202, 1716, 1240 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.84-0.90 (6H, m), 1.18-1.53 (28H, m), 1.70-1.77 (6H, m), 1.79-1.87 (7H, m), 2.07-2.14 (1H, m), 2.23-2.35 (2H, m), 3.56 (1H, s), 3.75-3.80 (1H, m), 3.87-3.88 (3H, s × 2: mixture of isomers), 4.02-4.03 (3H, s × 2: mixture of isomers), 4.04-4.09 (1H, m), 4.32 (2H, t, J = 6.8 Hz), 4.40 (2H, t, J = 6.8 Hz), 5.81-5.84 (1H, t × 2: mixture of isomers, J = 2.8 Hz), 7.21 (1H, t, J = 6.4 Hz), 7.25-7.31 (2H, m), 7.35 (2H, t. J = 6.4 Hz), 7.41-7.46 (2H, m), 7.50-7.54 (1H, m), 7.67 (1H, t, J = 7.8 Hz), 7.72-7.74 (1H, s × 2: mixture of isomers), 7.97-7.98 (1H, s × 2: mixture of isomers), 8.01 (1H, s), 8.13-8.14 (1H, s × 2: mixture of isomers), 8.16 (1H, s), 8.27-8.28 (2H, s × 2: mixture of isomers), 8.46-8.53 (3H, m), 8.69 (1H, d, J = 8.0 Hz), 8.80 (1H, d, J = 8.8 Hz). 13C NMR (100 MHz, CDCl3) δ 14.1, 18.5, 18.6, 22.6, 22.96, 23.02, 23.3, 23.4, 25.0, 26.02, 26.05, 28.59, 28.63, 29.3, 29.4, 29.49, 29.51, 29.53, 30.2, 31.8, 52.0, 52.1, 52.2, 52.3, 62.0, 62.1, 65.8, 65.9, 81.4, 84.3, 89.7, 89.8, 91.0, 92.4, 64.59, 94.64, 94.9, 96.8, 96.9, 116.1, 116.8, 116.9, 117.56, 117.59, 119.8, 120.10, 120.12, 122.1, 122.68, 122.70, 123.0, 123.6, 123.68, 123.74, 125.9, 126.52, 126.55, 126.8, 126.9, 127.1, 127.3, 127.6, 128.77, 128.80, 128.82, 128.88, 128.90, 129.19, 129.22, 129.4, 129.5, 129.68, 129.70, 129.73, 129.8, 130.0, 130.1, 130.55, 130.62, 130.8, 131.1, 131.3, 131.7, 132.4, 132.9, 133.0, 134.1, 136.3, 136.4, 136.9, 137.0, 138.3, 138.8, 138.9, 157.36, 157.41, 164.9, 165.5, 167.29, 167.33, 167.58, 38 ACS Paragon Plus Environment

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167.62. Trimer, (P)-2-OTHP (n = 3) Under

an

argon

atmosphere,

a

solution

of

(P)-5

(130

mg,

0.15

mmol),


mg,

0.28

mmol),


(55.4

mg,

0.14

mmol),

triphenylphosphine (37.4 mg, 0.14 mmol), and tetrabutylammonium iodide (664 mg, 1.8 mmol) in trietylamine (0.28 mL), N,N-dimethylformamide (1.8 mL), and tetrahydrofuran (1.8 mL) was freeze-evacuated three times. A solution of (P)-2-H-OTHP (n = 2) (83.3 mg, 0.062 mmol) in N,N-dimethylformamide (1.0 mL) and tetrahydrofuran (1.0 mL) was freeze-evacuated three times, and was added dropwise to the above mixture. The resluted mixture was stirred at 45 °C for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene = 1:1, 1:2, hexane:ethyl acetate = 8:1, 4:1, hexane:toluene:ethyl acetate =2:2:1), and GPC (toluene) gave (P)-2-OTHP (n = 3) (90.5 g, 0.044 mmol, 72 %) as a yellow solid. Mp 128-129 °C (CHCl3-methanol). [α]27D −154 (c 0.10, CHCl3). Anal. (C137H138O14Si) Calcd.: C, 80.79; H, 6.83. Found: C, 80.70; H, 6.94. IR (KBr) 2925, 2852, 2200, 2152, 1719, 1239, 783, 678 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.35 (9H, s), 0.82-0.90 (9H, m), 1.19-1.52 (42H, m), 1.59 (3H, s), 1.62-1.63 (3H, s × 2: mixture of isomers), 1.65-1.66 (3H, s × 2: mixture of isomers), 1.75-1.87 (12H, m), 1.89 (3H, s), 1.90 (3H, s), 2.09-2.17 (1H, m), 2.26-2.42 (2H, m), 3.77-3.89 (1H, m), 3.80 (3H, s × 2: mixture of isomers), 3.93 (3H, s × 2: mixture of isomers), 4.02 (3H, s × 2: mixture of isomer), 4.05-4.13 (1H, m), 4.34-4.37 (4H, m), 4.40 (2H, t, J = 7.0 Hz), 5.83-5.86 (1H, t × 2: mixture of isomers, J = 2.6 Hz), 7.04-7.03 (2H, m), 7.17-7.21 (2H, m), 7.23-7.29 (2H, m), 7.35 (1H, d, J = 7.2 Hz), 7.38 (1H, d, J = 7.6 Hz), 7.43-7.47 (2H, m), 7.53-7.58 (1H, m), 7.67 (1H, t, J = 7.8 Hz), 7.71-7.72 (1H, s × 2: mixture of isomers), 7.93 (1H, s), 7.93-7.94 (1H, s × 2: mixture of isomers), 8.01-8.02 (1H, s × 2: mixture of isomers), 8.10-8.11 (1H, s × 2: mixture of isomers), 8.17-8.18 (1H, s × 2: mixture of isomers), 8.22 (1H, s), 8.26 (1H, s), 8.29 (1H, s), 8.31-8.32 (1H, s × 2: mixture of isomers), 8.36-8.41 (2H, m), 8.43 (1H, s), 8.47-8.50 (2H, m), 8.54-8.56 (1H, d × 2: mixture of isomers, J = 7.6 Hz), 8.71 (1H, d, J = 8.0 Hz), 8.80 (1H, d, J = 8.4 Hz).

13

C NMR (100 MHz, CDCl3) δ −0.15, 14.07, 14.10, 18.6, 18.7, 22.6, 22.89, 22.93, 23.05,

23.07, 23.3, 23.4, 25.1, 26.0, 26.1, 28.66, 28.70, 29.3, 29.5, 30.3, 31.9, 51.97, 52.01, 52.26, 52.29, 62.0, 62.2, 65.8, 65.98, 65.95, 89.7, 89.8, 91.4, 92.32, 92.33, 92.4, 94.15, 94.18, 94.4, 94.76, 94.81, 94.85, 94.87, 95.0, 95.2, 95.3, 96.9, 97.0, 102.4, 102.678, 102.682, 116.2, 116.86, 116.93, 117.65, 117.69, 119.61, 119.64, 119.9, 120.119, 120.121, 122.5, 122.6, 122.7, 123.0, 123.35, 123.38, 123.46, 39 ACS Paragon Plus Environment


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124.49, 123.6, 123.7, 124.9, 125.8, 126.20, 126.21, 126.52, 126.54, 126.58, 126.85, 126.90, 127.1, 127.2, 127.3, 127.7, 128.75, 128.83, 128.85, 128.89, 129.1, 129.2, 129.27, 129.29, 129.4, 129.5, 129.73, 129.75, 129.82, 129.84, 129.98, 130.03, 130.1, 130.4, 130.5, 130.6, 130.7, 130.8, 131.0, 131.06, 131.10, 131.13, 131.4, 131.8, 132.19, 132.23, 132.4, 132.47, 132.49, 132.9, 134.3, 134.6, 134.7, 136.3, 136.5, 136.74, 136.77, 138.05, 138.13, 138.908, 138.912, 157.45, 157.48, 164.9, 165.1, 165.49, 165.52, 167.19, 167.23, 167.27, 167.30, 167.6, 167.7. Deprotected trimer, (P)-2-H-OTHP (n = 3) Under an argon atmosphere, to a solution of (P)-2-OTHP (n = 3) (90.5 mg, 0.044 mmol) in tetrahydrofuran (7.0 mL) was added a tetrahydrofuran solution of tetrabutylammonium fluoride (0.07 mL, 0.07 mmol) at 0 °C, and the mixture was stirred at 0 °C for 10 min. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene:ethyl acetate = 4:4:1) gave (P)-2-H-OTHP (n = 3) (95.2 mg, 0.044 mmol, 99%) as a yellow solid. Mp 114-115 °C (CH2Cl2-methanol). [α]27D −166 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C134H131NaO14 ([M+Na+H]+): 1986.94. Found: 1987.06. Anal. (C134H130O14) Calcd.: C, 81.93; H, 6.67. Found: C, 81.61; H, 6.86. IR (KBr) 2925, 2852, 2200, 1722, 1240, 783 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.81-0.92 (9H, m), 1.20-1.55 (42H, m), 1.62-1.63 (3H, s × 2: mixture of isomers), 1.66 (3H, s), 1.75-1.76 (3H, s × 2: mixture of isomers), 1.77-1.88 (12H, m), 1.89-1.90 (6H, s × 2: mixture of isomers), 2.10-2.16 (1H, m), 2.26-2.38 (2H, m), 3.606-3.609 (1H, s × 2: mixture of isomers), 3.78-3.79 (3H, s × 2: mixture of isomers), 3.78-3.85 (1H, m), 3.91-3.92 (3H, s × 2: mixture of isomers), 3.99-4.02 (3H, s × 2: mixture of isomers), 4.04-4.13 (1H, m), 4.36-4.40 (4H, m), 4.42 (2H, t, J = 7.0 Hz), 5.82-5.87 (1H, m), 7.05-7.13 (2H, m), 7.17-7.28 (4H, m), 7.34-7.39 (2H, m), 7.44-7.48 (2H, m), 7.55-7.59 (1H, m), 7.65-7.69 (1H, m), 7.72 (1H, s), 7.90-7.92 (1H, s × 2: mixture of isomers), 8.02-8.03 (1H, s × 2: mixture of isomers), 8.05-8.10 (2H, s × 3: mixture of isomers), 8.14-8.15 (1H, s × 2: mixture of isomers), 8.23 (1H, s), 8.28-8.31 (2H, s × 2: mixture of isomers), 8.34 (1H, s), 8.36-8.48 (5H, m), 8.56-8.57 (1H, d × 2: mixture of isomers, J = 7.6 Hz and 8.0 Hz), 8.71 (1H, d, J = 8.0 Hz), 8.81 (1H, d, J = 8.4 Hz). 13C NMR (100 MHz, CDCl3) δ 14.07, 14.09, 18.6, 18.7, 22.6, 22.7, 22.88, 22.92, 23.1, 23.30, 23.33, 23.4, 25.1, 26.0, 26.1, 28.6, 28.7, 29.3, 29.5, 29.6, 30.2, 31.9, 51.96, 52.01, 52.2, 52.3, 62.0, 62.2, 65.87, 65.94, 81.3, 84.6, 89.7, 89.8, 91.35, 91.37, 92.2, 92.3, 94.2, 94.31, 94.33, 94.78, 94.83, 94.90, 94.93, 95.29, 95.31, 96.9, 97.0, 116.2, 116.87, 116.93, 117.66, 117.69, 119.58, 119.61, 119.7, 120.10, 120.12, 122.5, 122.6, 122.65, 122.70, 123.0, 123.5, 123.6, 123.7, 125.4, 125.9, 126.18, 126.20, 126.50, 126.51, 126.54, 126.6, 40 ACS Paragon Plus Environment

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126.87, 126.90, 127.0, 127.1, 127.2, 127.3, 127.7, 128.75, 128.80, 128.82, 128.9, 129.1, 129.17, 129.24, 129.3, 129.4, 129.5, 129.7, 129.8, 129.98, 130.00, 130.04, 130.1, 130.4, 130.5, 130.6, 130.7, 130.9, 131.02, 131.04, 131.1, 131.37, 131.38, 131.8, 132.18, 132.21, 132.4, 132.5, 132.9, 134.3, 134.66, 134.72, 136.3, 136.5, 136.76, 136.77, 137.00, 137.02, 137.05, 138.1, 138.3, 138.9, 157.46, 157.49, 164.86, 164.89, 165.48, 165.50, 167.17, 167.21, 167.22, 167.25, 167.6, 167.7. Tetramer, (P)-2-OTHP (n = 4) Under

an

argon

atmosphere,

a

solution

of

(P)-5

(75.9

mg,

0.09

mmol),


mg,

0.14

mmol),


(26.8

mg,

0.069

mmol),

triphenylphosphine (18.1 mg, 0.069 mmol), and tetrabutylammonium iodide (321 mg, 0.87 mmol) in trietylamine (0.25 mL), N,N-dimethylformamide (1.5 mL), and tetrahydrofuran (1.5 mL) was freeze-evacuated three times. A solution of (P)-2-H-OTHP (n = 3) (59 mg, 0.03 mmol) in N,N-dimethylformamide (1.0 mL) and tetrahydrofuran (1.0 mL) was freeze-evacuated three times, and was added dropwise to the above mixture. The resulted mixture was stirred at 45 °C for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene = 1:1, 1:2, hexane:toluene:ethyl acetate =2:2:1) and GPC(toluene) gave (P)-2-OTHP (n = 4) (57 mg, 0.02 mmol, 71 %) 148-149

°C

(CH2Cl2-methanol).

[α]27D

−78

(c

0.10,

as a yellow solid. Mp

CHCl3).

MALDI-TOF

MS

(α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C180H178NaO18Si+ ([M+Na]+): 2678.27. Found: 2678.30. Anal. (C180H178O18Si) Calcd.: C, 81.35; H, 6.75. Found: C, 81.17; H, 6.95. IR (KBr) 2926, 2360, 1716, 1507 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.35-0.36 (9H, s × 2: mixture of isomers), 0.81-0.91 (12H, m), 1.21-1.51 (56H, m), 1.55 (3H, s × 2: mixture of isomers), 1.62-1.63 (3H, s × 2: mixture of isomers), 1.67 (3H, s × 2: mixture of isomers), 1.75-1.90 (26H, m), 2.10-2.17 (1H, m), 2.27-2.38 (2H, m), 3.74-3.90 (1H, m), 3.79-3.80 (3H, s × 2: mixture of isomers), 3.84-3.85 (3H, s × 2: mixture of isomers), 3.93-3.94 (3H, s × 2: mixture of isomers), 4.00-4.02 (3H, s × 2: mixture of isomers), 4.04-4.13 (1H, m), 4.38-4.43 (8H, m), 5.83-5.87 (1H, m), 7.06-7.31 (11H, m), 7.35-7.40 (2H, m), 7.44-7.49 (2H, m), 7.54-7.58 (1H, m), 7.66-7.74 (2H, m), 7.89-7.92 (1H, s × 2: mixture of isomers), 7.95-7.98 (1H, s × 2: mixture of isomers), 8.02-8.03 (2H, s × 2: mixture of isomers), 8.09-8.14 (2H, s × 3: mixture of isomers), 8.18-8.23 (2H, s × 2: mixture of isomers), 8.23-8.32 (4H, s × 4: mixture of isomers), 8.39-8.50 (7H, m), 8.55-8.56 (1H, d × 2: mixture of isomers, J = 6.8 Hz and 7.2 Hz), 8.73 (1H, d, J = 8.0 Hz), 8.81 (1H, d, J = 8.4 Hz).

13

C NMR (100 MHz, CDCl3) δ

−0.13, 14.10. 14.12, 18.6, 18.7, 22.7, 22.85, 22.91, 22.96, 23.1, 23.3, 23.4, 25.1, 26.0, 26.1, 28.69, 41 ACS Paragon Plus Environment


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Page 42 of 51

28.72, 28.8, 29.3, 29.6, 30.3, 31.9, 52.0, 52.1, 52.17, 52.29, 52.3, 62.1, 62.2, 65.87, 65.90, 66.02, 89.7, 89.8, 91.40, 91.41, 92.19, 92.22, 92.3, 92.38, 92.39, 94.05, 94.09, 94.55, 94.58, 94.76, 94.78, 94.83, 94.93, 94.96, 95.0, 95.40, 95.43, 95.6, 96.9, 97.0, 102.4, 102.8, 116.17, 116.20, 116.91, 116.98, 117.70, 117.74, 119.57, 119.63, 119.7, 119.9, 120.2, 122.6, 122.8, 123.0, 123.3, 123.39, 123.45, 123.48, 123.53, 123.67, 123.74, 124.9, 125.3, 126.0, 126.3, 126.6, 126.7, 126.9, 127.0, 127.08, 127.14, 127.4, 127.7, 128.7, 128.8, 128.87, 128.93, 129.1, 129.17, 129.24, 129.3, 129.4, 129.5, 129.6, 129.8, 129.861, 129.862, 130.05, 130.07, 130.14, 130.48, 130.50, 130.54, 130.61, 130.64, 130.7, 130.8, 131.07, 131.10, 131.14, 131.2, 131.3, 131.4, 131.8, 132.21, 132.24, 132.3, 132.4, 132.50, 132.51, 133.00, 133.02, 134.4, 134.76, 134.84, 134.87, 134.89, 136.30, 136.34, 136.5, 136.81, 136.82, 136.88, 136.89, 137.1, 138.1, 138.2, 139.0, 157.50, 157.53, 164.88, 164.92, 165.2, 165.51, 167.53, 167.18, 167.21, 167.28, 167.31, 167.37, 167.40, 167.69, 167.73. Deprotected tetramer, (P)-2-H-OTHP (n = 4) Under an argon atmosphere, to a solution of (P)-2-OTHP (n = 4) (57 mg, 0.02 mmol) in tetrahydrofuran (5.0 mL) was added a tetrahydrofuran solution of tetrabutylammonium fluoride (0.03 mL, 0.03 mmol) at 0 °C, and the mixture was stirred at 0 °C for 10 min. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene:ethyl acetate = 2:2:1) gave (P)-2-H-OTHP (n = 4) (54.0 mg, 0.02 mmol, 99%) as a yellow solid. Mp 140-141 °C (CH2Cl2-methanol). [α]27D +424 (c 0.90, CHCl3). Anal. (C177H170O18) Calcd.: C, 82.23; H, 6.63. Found: C, 81.81; H, 6.76. IR (KBr) 2924, 2360, 1717, 1240 cm−1.

1

H NMR (400 MHz, CDCl3) δ 0.82-0.92 (12H, m), 1.21-1.53 (56H, m), 1.54-1.55 (3H,

s × 2: mixture of isomers), 1.62-1.63 (3H, s × 2: mixture of isomers), 1.68 (3H, s × 2: mixture of isomers), 1.75-1.90 (26H, m), 2.04-2.17 (1H, m), 2.26-2.38 (2H, m), 3.60 (1H, s × 2: mixture of isomers), 3.74-3.82 (1H, m), 3.79-3.80 (3H, s × 2: mixture of isomers), 3.84-3.85 (3H, s × 2: mixture of isomers), 3.93-3.94 (3H, s × 2: mixture of isomers), 4.01-4.02 (3H, s × 2: mixture of isomers), 4.04-4.13 (1H, m), 4.36-4.44 (8H, m), 5.83-5.87 (1H, m), 7.06-7.30 (11H, m), 7.35-7.40 (2H, m), 7.44-7.48 (2H, m), 7.54-7.57 (1H, m), 7.65-7.74 (2H, m), 7.91-7.93 (1H, s × 2: mixture of isomers), 7.96-7.98 (1H, s × 2: mixture of isomers), 8.02-8.03 (1H, s × 2: mixture of isomers), 8.05 (1H, s), 8.10-8.15 (2H, s × 4: mixture of isomers), 8.18-8.20 (1H, s × 2: mixture of isomers), 8.23 (1H, s × 2: mixture of isomers), 8.29-8.34 (4H, m), 8.39-8.50 (7H, m), 8.55-8.56 (1H, d × 2: mixture of isomers, J = 8.0 Hz), 8.71 (1H, d, J = 8.0 Hz), 8.81 (1H, d, J = 8.0 Hz). 13C NMR (100 MHz, CDCl3) δ 14.1, 18.6, 18.7, 22.7, 22.85, 22.9, 23.0, 23.1, 23.3, 23.4, 23.5, 25.1, 26.06, 26.11, 28.64, 28.73, 28.8, 29.3, 29.56, 29.58, 29.7, 30.3, 31.9, 52.0, 52.1, 52.2, 52.28, 52.32, 62.1, 62.2, 42 ACS Paragon Plus Environment

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65.9, 66.00, 66.04, 81.3, 84.6, 89.7, 89.8, 91.39, 91.41, 92.17, 92.18, 92.24, 92.3, 94.21, 94.22, 94.51, 94.53, 94.60, 94.62, 94.78, 94.83, 95.0, 95.3, 95.38, 95.44, 95.6, 96.9, 97.1, 116.17, 116.20, 116.9, 117.0, 117.71, 117.74, 119.5, 119.62, 119.64, 119.8, 120.2, 122.6, 122.7, 122.8, 123.0, 123.2, 123.4, 123.5, 123.7, 125.3, 125.4, 126.0, 126.3, 126.7, 126.92, 126.94, 127.1, 127.2, 127.4, 127.7, 128.76, 128.82, 128.89, 128.93, 129.1, 129.17, 129.19, 129.24, 129.4, 129.5, 129.6, 129.8, 129.9, 130.05, 130.09, 130.14, 130.48, 130.50, 130.58, 130.64, 130.7, 130.9, 131.0, 131.07, 131.10, 131.2, 131.3, 131.4, 131.9, 132.20, 132.24, 132.3, 132.4, 132.5, 133.0, 134.4, 134.76, 134.81, 134.89, 134.91, 136.30, 136.34, 136.5, 136.8, 136.9, 137.07, 137.11, 138.1, 138.4, 139.0, 157.50, 157.54, 164.87, 164.90, 165.2, 165.5, 167.19, 167.21, 167.28, 167.31, 167.35, 167.36, 167.70, 167.74. Tetramer derivative, (P)-22 Under

an

argon

atmosphere,

a

solution

of

19

(24.5

mg,

0.06

mmol),

tris(dibenzylidenacetone)dipalladium(0) chloroform adduct (5.4 mg, 0.005 mmol), cuprous iodide (12.0mg, 0.06 mmol), tris(2,4,6-trimethylphenyl)phosphine (12.2 mg, 0.032 mmol), and tetrabutylammonium

iodide

(155

mg,

0.42

mmol)

in

trietylamine

(0.25

mL),

N,N-dimethylformamide (1.5 mL), and tetrahydrofuran (1.5 mL) was freeze-evacuated three times. A solution of (P)-2-H-OTHP (n = 4) (54 mg, 0.02 mmol) in N,N-dimethylformamide (1.0 mL) and tetrahydrofuran (1.0 mL) was freeze-evacuated three times, and was added dropwise to the above mixture. The resulted mixture was stirred at room temperature for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene = 1:1, 1:2, hexane:toluene:ethyl acetate =1:1:1) and GPC (toluene) gave (P)-22 (49 mg, 0.02 mmol, 82 %) as a yellow solid. Mp 126-127 °C (CH2Cl2-methanol). [α]27D −117 (c 0.10, CHCl3). Anal. (C194H194O20) Calcd.: C, 81.88; H, 6.87. Found: C, 81.92; H, 6.92. IR (KBr) 2924, 2360, 1716, 1507 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.82-0.92 (15H, m), 1.21-1.51 (70H, m), 1.54-1.55 (3H, s × 2: mixture of isomers), 1.62-1.63 (3H, s × 2: mixture of isomers), 1.68 (3H, s), 1.75-1.90 (28H, m), 2.04-2.17 (1H, m), 2.26-2.35 (2H, m), 3.80 (4H, m), 3.85 (3H, s × 2: mixture of isomers), 3.94 (3H, s), 4.02 (3H, s × 2: mixture of isomers), 4.04-4.13 (1H, m), 4.35-4.47 (10H, m), 5.84-5.87 (1H, m), 7.05-7.30 (9H, m), 7.34-7.47 (5H, m), 7.51 (1H, t, J = 7.8 Hz), 7.57 (1H, t, J = 7.6 Hz), 7.68 (1H, t, J = 7.8 Hz), 7.73-7.74 (1H, s × 2: mixture of isomers), 7.83 (1H, dt, J = 1.4, 8.0 Hz), 7.92-7.93 (1H, s × 2: mixture of isomers), 7.98-7.99 (1H, s × 2: mixture of isomers), 8.03 (1H, s × 2: mixture of isomers), 8.08 (1H, dt, J = 1.4, 8.0 Hz), 8.11-8.15 (3H, s × 4: mixture of isomers), 8.19-8.20 (1H, s × 2: mixture of isomers), 8.23 (1H, s), 8.30-8.32 (3H, s × 3: mixture of isomers), 8.34-8.35 (1H, s × 2: mixture of isomers), 8.40-8.51 (9H, m), 8.54-8.55 (1H, d × 2: 43 ACS Paragon Plus Environment


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mixture of isomers, J = 8.0 Hz), 8.74 (1H, d, J = 8.0 Hz), 8.80 (1H, d, J = 8.0 Hz). 13C NMR (100 MHz, CDCl3) δ 14.1, 18.6, 18.7, 22.6, 22.8, 22.87, 22.91, 22.99, 23.03, 23.3, 23.4, 25.1, 26.0, 26.1, 28.7, 28.8, 29.26, 29.31, 29.5, 30.3, 31.7, 31.8, 51.9, 52.0, 52.05, 52.10, 52.20, 52.25, 62.1, 62.2, 65.4, 65.8, 65.9, 66.0, 88.5, 89.7, 89.8, 89.9, 91.4, 92.2, 92.3, 92.4, 94.2, 94.26, 94.29, 94.31, 94.6, 94.8, 94.9, 95.0, 95.1, 95.2, 95.3, 95.4, 95.55, 95.58, 95.63, 95.7, 96.9, 97.0, 116.2, 116.8, 117.0, 117.6, 117.7, 119.5, 119.58, 119.61, 119.7, 119.8, 120.1, 120.2, 122.59, 122.64, 122.7, 123.0, 123.2, 123.3, 123.38, 123.43, 123.5, 123.7, 124.9, 125.3, 125.9, 126.17, 126.23, 126.5, 126.56, 126.59, 126.9, 127.0, 127.3, 127.7, 128.5, 128.77, 128.83, 128.9, 129.19, 129.24, 129.3, 129.5, 129.70, 129.75, 129.79, 130.0, 130.1, 130.4, 130.6, 130.66, 130.69, 130.86, 130.91, 131.0, 131.07, 131.12, 131.2, 131.4, 132.17, 132.21, 132.3, 132.4, 132.48, 132.52, 132.8, 133.00, 133.04, 134.7, 134.8, 135.0, 135.8, 136.3, 136.5, 136.7, 136.77, 136.84, 136.9, 137.01, 137.04, 137.57, 137.60, 138.0, 138.8, 138.9, 157.4, 157.5, 164.8, 165.0, 165.4, 165.5, 165.8, 167.0, 167.1, 167.2, 167.3, 167.5, 167.6. Tetramer derivative, (P)-6 Under an argon atmosphere, a solution of (P)-22 (n = 4) (93 mg, 0.03 mmol), p-toluenesulfonic acid monohydrate (25 mg, 0.131 mmol) in dichloromethane (12.0 mL) and methanol (12.0 mL) was stirred at room temperature for 6 h. The reaction was quenched by adding water, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane: toluene: ethyl acetate = 2:2:1) gave (P)-6 (88.0 mg, 0.03 mmol, 97 %) as a yellow solid. Mp 127-128 °C (CH2Cl2-methanol). [α]27D −90 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C189H187O19+ ([M+H]+): 2760.37. Found: 2763.95. Anal. (C189H186O19) Calcd.: C, 82.20; H, 6.79. Found: C, 81.93; H, 6.92. IR (KBr) 2925, 2359, 1716, 1507 cm−1. 1H NMR (400 MHz, CDCl3) δ 0.81-0.92 (15H, m), 1.21-1.50 (70H, m), 1.56 (6H, s), 1.67 (3H, s), 1.71 (3H, s), 1.75-1.87 (22H, m), 3.83 (3H, s), 3.90 (3H, s), 3.93 (3H, s), 4.07 (3H, s), 4.33-4.41 (8H, m), 4.44 (2H, t, J = 7.0 Hz), 6.40 (1H, br s), 7.11-7.32 (10H, m), 7.36-7.40 (3H, m), 7.45 (1H, d, J = 6.8 Hz), 7.50 (1H, dd, J = 7.6, 8.0 Hz), 7.57 (1H, dd, J = 7.2, 8.0 Hz), 7.68 (1H, dd, J = 7.2, 8.4 Hz), 7.81-7.84 (2H, m), 7.86 (1H, s), 7.93 (1H, s), 7.95 (1H, s), 8.08 (1H, dt, J = 1.5, 7.6 Hz), 8.09-8.10 (2H, m), 8.11 (1H, s), 8.15 (1H, d, J = 8.0 Hz), 8.18 (1H, s), 8.28 (2H, s), 8.31 (2H, s), 8.34 (1H, s), 8.39-8.49 (4H, m), 8.39 (1H, s), 8.46 (1H, s), 8.48 (1H, s), 8.51 (1H, s), 8.55 (1H, d, J = 8.0 Hz), 8.73 (1H, d, J = 7.6 Hz), 8.82 (1H, d, J = 8.0 Hz).

13

C NMR (100 MHz, CDCl3) δ 14.1, 22.7, 22.8, 22.9, 22.91, 23.0, 23.1, 23.30, 23.33, 23.37,

23.41, 26.0, 26.1, 28.69, 28.72, 28.76, 28.79, 29.3, 29.55, 29.59 29.7, 31.9, 52.1, 52.2, 52.3, 52.4, 65.5, 65.96, 66.02, 66.1, 86.8, 88.5, 91.2, 92.2, 92.3, 92.4, 94.2, 94.5, 94.7, 94.8, 95.2, 95.4, 95.6, 44 ACS Paragon Plus Environment

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95.7, 97.2, 114.3, 115.5, 117.6, 118.7, 119.6, 119.7, 119.8, 122.6, 122.8, 123.0, 123.1, 123.3, 123.40, 123.44, 123.6, 123.7, 124.9, 125.3, 126.0, 126.3, 126.4, 126.7, 127.0, 127.1, 127.2, 127.35, 127.41, 127.6, 127.7, 128.6, 128.76, 128.81, 129.06, 129.11, 129.18, 129.21, 129.3, 129.4, 129.5, 129.56, 129.60, 129.8, 129.9, 130.0, 130.07, 130.09, 130.3, 130.5, 130.59, 130.61, 130.7, 130.90, 130.95, 131.1, 131.17, 131.24, 131.27, 131.31, 131.34, 131.9, 132.22, 132.24, 132.5, 132.8, 133.8, 134.6, 134.7, 135.0, 135.9, 136.31, 136.35, 136.36, 136.6, 136.85, 136.90, 137.1, 137.2, 137.6, 137.9, 138.1, 138.4, 156.6, 164.9, 165.1, 165.2, 165.9, 167.2, 167.4, 167.5, 167.7. 16-Bromohexadecyl 3-iodobenzoate, 23 Under an argon atmosphere, a solution of 3-iodobenzoic acid (200 mg, 0.81 mmol), and potassium carbonate (224 mg, 1.62 mmol) in N,N-dimethylformamide (3 mL) was added 1,16-dibromodecane (771 mg, 1.61 mmol) at room temperature, and the mixture was stirred at 60 °C for 1 h. The reaction was quenched by adding water, and the organic materials were extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane only, hexane:ethyl acetate = 30:1) gave 20 (398 mg, 0.74 mmol, 91%) as a colorless solid. Mp. 235-236 °C (CHCl3-methanol). LRMS (EI) m/z 552.0 (M+2, 4.7%), 550.0 (M+, 4.8%), 247.9 ([C7H3IO2]+, 100%), 230.9 ([M−C16H32BrO]+, 5.8%). HRMS (EI) m/z Calcd. for C23H36BrIO2 (M+2): 552.0943. Found: 552.0954. IR (KBr) 2921, 2848, 1712, 1469, 1293, 1255, 742 cm−1. 1H NMR (400 MHz, CDCl3) δ 1.26-1.44 (24H, m), 1.76 (2H, quint, J = 7.1 Hz), 1.85 (2H, quint, J = 7.2 Hz), 3.41 (2H, t, J = 6.8 Hz), 4.31 (2H, t, J = 6.8 Hz), 7.18 (1H, ddd, J = 0.4, 7.6, 7.8 Hz), 7.88 (1H, ddd, J = 1.2, 1.8, 7.8 Hz), 8.00 (1H, ddd, J = 1.2, 1.6, 7.6 Hz), 8.37 (1H, t, J = 1.6 Hz). 13C NMR (100 MHz, CDCl3) δ 25.9, 28.1, 28.6, 28.7, 29.2, 29.38, 29.45, 29.49, 29.52, 29.6, 32.8, 34.0, 65.5, 93.7, 128.6, 129.9, 132.3, 138.3, 141.5, 165.1. Linker 7 Under an argon atmosphere, a solution of isophthalic acid (30.0 mg, 0.18 mmol), and potassium carbonate (15.1 g, 0.18 mmol) in N,N-dimethylformamide (7 mL) was added 23 (20 mg, 0.36 mmol) at room temperature, and the mixture was stirred at 90 °C for 1 h. The reaction was quenched by adding 4 M hydrochloric acid, and the organic materials were extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane only, hexane:ethyl acetate = 8:1, 1:1) gave 7 (14.4 mg, 0.08 mmol, 63%) as a colorless solid. Mp 107-108 °C (CH2Cl2-methanol). LRMS (EI) m/z 636.1 (M+, 6.6%), 247.9 ([C7H3IO2]+, 100%), 222.2 ([C16H30]+, 71%). HRMS (EI) m/z Calcd. for C31H41IO6 (M+): 636.1948. Found: 636.1952. IR 45 ACS Paragon Plus Environment


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(KBr) 2918, 2850, 1714, 1477, 1300, 1258, 729 cm−1. 1H NMR (400 MHz, CDCl3) δ 1.26-1.48 (24H, m), 1.76 (2H, quint, J = 7.2 Hz), 1.79 (2H, quint, J = 7.0 Hz), 4.31 (2H, t, J = 6.6 Hz), 4.36 (2H, t, J = 6.6 Hz), 7.18 (1H, t, J = 7.8 Hz), 7.58 (1H, t, J = 7.8 Hz), 7.88 (1H, ddd, J = 1.2, 1.8. 7.8 Hz), 8.00 (1H, ddd, J = 1.2, 1.6, 8.0 Hz), 8.29 (2H, dd, J = 1.8, 7.8 Hz), 8.37 (1H, t, J = 1.8 Hz), 8.75 (1H, dd, J = 1.2, 1.6 Hz). 13C NMR (100 MHz, CDCl3) δ 25.6, 25.96, 25.98, 28.6, 28.7, 29.2, 29.3, 29.5, 29.56, 29,62, 29.64, 65.59, 65.62, 67.9, 93.8, 128.7, 129.8, 130.0, 131.1, 131.3, 132.4, 134.2, 134.6, 138.4, 141.6, 165.2, 165.7, 170.4. Tetramer connected to linker, (P)-8 Under an argon atmosphere, to a solution of (P)-6 (33.2 mg, 0.012 mmol) and 7 (15.3 mg, 0.024 mmol) in dichloromethane (3.0 mL) was added N,N’-dicyclohexylcarbodiimide (12.4 mg, 0.06 mmol), and N,N’-dimethyl-4-aminopyridine (2.9 mg, 0.024 mmol) at room temperature, and the mixture was stirred at 40 °C for 4 h. The reaction was quenched by adding H2O, and the organic materials were extracted with dichloromethane. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene = 1:1 and 1:2, hexane:toluene:ethyl acetate = 2:2:1), and GPC (toluene) gave (P)-8 (25.0 mg, 0.007 mmol, 62 %) as a yellow solid. Mp 101-102 °C (CH2Cl2-methanol). [α]27D −24 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C220H225INaO24 ([M+Na]+): 3400.53. Found: 3400.24. Anal. (C220H225IO24) Calcd.: C, 78.18; H, 6.71. Found: C, 78.16; H, 6.86. IR (KBr) 2924, 2853, 1723, 1463, 1240 cm−1. 1

H NMR (400 MHz, CDCl3) δ 0.81-0.90 (15H, m), 1.20-1.49 (94H, m), 1.56 (3H, s), 1.58 (3H, s),

1.68 (3H, s), 1.72-1.87 (29H, m), 3.82 (3H, s), 3.85 (3H, s), 3.94 (3H, s), 4.03 (3H, s), 4.30 (2H, t, J = 6.6 Hz), 4.34-4.42 (10H, m), 4.45 (2H, t, J = 6.8 Hz), 6.86 (1H, t, J = 7.6 Hz), 7.08-7.21 (11H, m), 7.22-7.30 (2H, m), 7.40 (1H, d, J = 7.6 Hz), 7.42 (1H, d, J = 8.0 Hz), 7.51 (1H, t, J = 7.8 Hz), 7.55 (1H, s), 7.58 (1H, t, J = 7.6 Hz), 7.65 (1H, dd, J = 7.2, 8.4 Hz), 7.72 (1H, t, J = 7.8 Hz), 7.83 (1H, dt, J = 1.4, 8.0 Hz), 7.86 (1H, ddd, J = 1.2, 1.6, 8.0 Hz), 7.92 (1H, s), 7.95 (1H, d, J = 8.4 Hz), 7.98 (1H, s), 7.99 (1H, dt, J = 1.4, 8.0 Hz), 8.01 (1H, s), 8.08 (1H, dt, J = 1.4 Hz), 8.11 (1H, s), 8.14 (1H, s), 8.16 (1H, s), 8.20 (1H, s), 8.30 (1H, s), 8.31-8.36 (4H, m), 8.40 (1H, s), 8.41-8.51 (9H, m), 8.61 (1H, dt, J = 1.5, 8.0 Hz), 8.74 (1H, d, J = 8.0 Hz), 8.78 (1H, d, J = 8.4 Hz), 9.11 (1H, t, J = 1.6 Hz).13C NMR (100 MHz, CDCl3) δ 14.1, 22.6, 22.8, 22.9, 23.30, 23.34, 25.9, 26.0, 26.08, 26.11, 28.59, 28.62, 28.67, 28.70, 28.8, 29.2, 29.29, 29.31, 29.34, 29.46, 29.54, 29.58, 29.62, 31.9, 52.0, 52.1, 52.2, 52.3, 65.46, 65.52, 65.8, 65.9, 66.0, 66.1, 88.0, 88.5, 92.1, 92.2, 92.4, 93.3, 93.7, 93.9, 94.2, 94.5, 94.81, 94.84, 95.2, 95.6, 95.7, 96.4, 119.1, 119.5, 119.8, 121.6, 122.0, 122.6, 122.8, 123.0, 123.1, 123.2, 123.35, 123.39, 123.6, 123.7, 124.9, 125.3, 125.4, 126.3, 126.6, 126.8, 127.08, 127.14, 127.3, 127.4, 127.5, 127.7, 128.55, 128.65, 128.74, 128.8, 128.9, 129.07, 129.12, 129.16, 46 ACS Paragon Plus Environment

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129.23, 129.3, 129.4, 129.50, 129.53, 129.9, 130.0, 130.06, 130.09, 130.2, 130.4, 130.47, 130.5, 130.6, 130.7, 130.89, 130.94, 131.06, 131.08, 131.17, 131.24, 131.3, 131.6, 131.9, 132.2, 132.3, 132.4, 132.6, 132.8, 134.6, 135.0, 135.8, 136.29, 136.33, 136.5, 136.87, 136.93, 137.1, 137.6, 138.1, 138.3, 139.1, 141.6, 151.0, 163.6, 164.5, 164.8, 164.9, 165.0, 165.1, 165.4, 165.9, 167.2, 167.26, 167.34, 167.6. Head-to-tail bis(tetramer), (P)-3 Under

an

argon

atmosphere,

a

solution

of

(P)-8

(25.0

mg,

0.007

mmol),

tris(dibenzylidenacetone)dipalladium(0) chloroform adduct (2.6 mg, 0.003 mmol), cuprous iodide (4.2 mg, 0.02 mmol), tris(2,4,6-trimethylphenyl)phosphine (4.3 mg, 0.01 mmol), and tetrabutylammonium

iodide

(54.7

mg,

0.15

mmol)

in

trietylamine

(0.38

mL),

N,N-dimethylformamide (1.5 mL), and tetrahydrofuran (3.0 mL) was freeze-evacuated three times. A solution of (P)-2-H (n = 4) (18.6 mg, 0.007 mmol) in N,N-dimethylformamide (1.0 mL) and tetrahydrofuran (2.0 mL) was freeze-evacuated three times, and was added dropwise to the above mixture. The resultedmixture was stirred at 30 °C for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure giving, and purification by silica gel chromatography (hexane: toluene = 1:1, hexane:toluene: ethyl acetate = 4:4:1, 2:2:1, and 1:1:1), and GPC (tetrahydrofuran) gave (P)-3 (11.0 mg, 0.002 mmol, 24 %) as a yellow solid. Mp 150-152 °C (CH2Cl2-methanol). [α]27D −52 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C393H388NaO41 ([M+Na]+): 5785.82. Found: 5785.86. Anal. (C393H388O41) Calcd.: C, 81.84; H, 6.78. Found: C, 81.55; H, 7.06. IR (KBr) 2924, 2360, 1716, 1541 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.80-0.89 (27H, m), 1.19-1.50 (150H, m), 1.56 (6H, s), 1.67 (6H, s), 1.75-1.87 (58H, m), 3.81 (3H, s), 3.82 (3H, s), 3.829 (3H, s), 3.833 (3H, s), 3.925 (3H, s), 3.930 (3H, s), 4.02 (3H, s), 4.03 (3H, s), 4.19 (3H, s), 4.28-4.46 (22H, m), 6.86 (1H, t, J = 7.6 Hz), 6.99 (1H, d, J = 7.2 Hz), 7.09-7.35 (20H, m), 7.37-7.45 (6H, m), 7.48-7.59 (6H, m), 7.62-7.74 (6H, m), 7.82-7.83 (3H, m), 7.87 (1H, s), 7.90 (1H, s), 7.94-7.97 (3H, m), 8.00 (1H, s), 8.06-8.22 (11H, m), 8.29-8.33 (8H, m), 8.39-8.50 (18H, m), 8.60 (1H, d, J = 8.4 Hz), 8.73 (2H, d, J = 7.6 Hz), 8.78 (1H, d, J = 8.0 Hz), 8.81 (1H, d, J = 8.4 Hz), 9.10 (1H, s). 13C NMR (150 MHz, CDCl3) δ 14.1, 22.7, 22.7, 22.9, 23.0, 23.1, 23.3, 23.4, 23.4, 25.9, 26.0, 26,1, 26.1, 28.7, 28.8, 29.3, 29.3, 29.6, 29.6, 29.7, 29.7, 31.9, 52.1, 52.1, 52.3, 52.4, 56.5, 65.5, 65.8, 66.0, 66.1, 88.0, 88.5, 89.5, 91.4, 92.2, 92.4, 94.2, 94.2, 94.6, 94.8, 95.2, 95.5, 95.7, 96.4, 115.6, 117.1, 119.1, 119.6, 122.0, 122.6, 122.8, 123.0, 123.4, 123.6, 123.7, 124.9, 126.4, 126.7, 126.9, 127.1, 127.2, 127.3, 127.7, 128.6, 128.8, 128.9, 129.2, 129.4, 129.6, 129.8, 129.9, 130.1, 130.2, 130.2, 130.4, 130.5, 130.6, 130.7, 130.8, 131.0, 131.1, 131.2, 131.3, 131.4, 131.5, 131.7, 47 ACS Paragon Plus Environment


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132.3, 132.5, 132.6, 132.9, 134.7, 135.0, 135.9, 136.3, 136.4, 136.6, 136.9, 137.1, 137.6, 138.1, 139.2, 151.0, 160.0, 164.9, 165.0, 165.0, 165.5, 165.6, 165.9, 167.2, 167.3, 167.4, 167.6, 167.8. Because of complex spectrum, all the peaks could not be identified. Head-to-head bis(tetramer), (P)-4 Under an argon atmosphere, a solution of 1,18-bis(3-iodophenyl) esterS2 (7.6 mg, 0.01 mmol), tris(dibenzylidenacetone)dipalladium(0) chloroform adduct (7.0 mg, 0.007 mmol), cuprous iodide (11.4 mg, 0.06 mmol), tris(2,4,6-trimethylphenyl)phosphine (11.7 mg, 0.03 mmol), and tetrabutylammonium

iodide

(148

mg,

0.4

mmol)

in

trietylamine

(0.12

mL),

N,N-dimethylformamide (1.5 mL), and tetrahydrofuran (3.0 mL) was freeze-evacuated three times. A solution of (P)-2-H (n = 4) (50 mg, 0.02 mmol) in N,N-dimethylformamide (1.0 ml) and tetrahydrofuran (2.0 ml) was freeze-evacuated three times, and was added dropwise to the above mixture. The resulted mixture was stirred at room temperature for 4 h. The reaction was quenched by adding saturated aqueous ammonium chloride, and the organic materials were extracted with toluene. The organic layer was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and purification by silica gel chromatography (hexane:toluene = 1:1, hexane:toluene: ethyl acetate = 3:3:1, 2:2:1, and 1:1:1), and GPC (tetrahydrofuran) gave (P)-4 (26.3 mg, 0.005 mmol, 24 %) as a yellow solid. Mp 154-156 °C (CH2Cl2-methanol). [α]27D −76 (c 0.10, CHCl3). MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid) m/z Calcd. for C376H366NaO38 ([M+Na]+): 5511.66. Found: 5511.30. Anal. (C376H366O38) Calcd.: C, 82.22; H, 6.72. Found: C, 82.20; H, 6.72. IR (KBr) 2923, 2850, 2201, 1721, 1239, 783 cm−1. 1H-NMR (400 MHz, CDCl3) δ 0.80-0.89 (24H, m), 1.18-1.48 (136H, m), 1.57 (6H, s), 1.59 (6H, s), 1.68 (6H, s), 1.75-1.87 (50H, m), 3.83 (6H, s), 3.84 (6H ,s), 3.93 (6H, s), 4.04 (6H, s), 4.19 (6H, s), 4.34-4.46 (16H, m), 4.44 (4H, t, J = 6.6 Hz), 7.09-7.22 (18H, m), 7.28-7.34 (6H, m), 7.39-7.44 (6H, m), 7.50 (2H, t, J = 7.8 Hz), 7.57 (2H, t, J = 7.6 Hz), 7.66 (2H, t, J = 7.8 Hz), 7.74 (2H, s), 7.82 (2H, d, J = 8.0 Hz), 7.84 (2H, s), 7.89 (2H, s), 7.97 (2H, s), 8.07 (2H, dt, J = 1.4, 7.6 Hz), 8.10 (2H, s), 8.12 (2H, s), 8.19-8.22 (6H, m), 8.29-8.31 (6H, m), 8.34 (2H, s), 8.39-8.48 (16H, m), 8.51 (2H, s), 8.73 (2H, d, J = 8.0 Hz), 8.81 (2H, d, J = 8.4 Hz). 13C NMR (100 MHz, CDCl3) δ 14.1, 22.6, 22.7, 22.9, 23.0, 23.1, 23.3, 23.36, 23.42, 26.0, 26.1, 28.7, 29.3, 29.56, 29.59, 29.63, 29.7, 31.9, 52.08, 52.13, 52.26, 52.32, 56.4, 65.5, 65.9, 66.02, 66.05, 88.5, 89.5, 91.4, 92.21, 92.25, 92.4, 94.2, 94.56, 94.59, 94.8, 94.9, 95.2, 95.3, 95.5, 95.6, 95.7, 112.7, 115.6, 117.1, 119.58, 119.63, 119.9, 120.0, 122.6, 122.7, 122.8, 123.0, 123.3, 123.4, 123.5, 123.56, 123.64, 123.7, 124.9, 125.3, 126.0, 126.3, 126.4, 126.7, 127.1, 127.2, 127.3, 127.7, 128.6, 128.8,128.9, 129.0, 129.15, 129.24, 129.4, 129.5, 129.6, 129.8, 129.9, 130.1, 130.49, 130.52, 130.6, 130.7, 130.9, 131.0, 131.1, 131.29, 131.31, 131.4, 132.2, 132.3, 132.46, 132.54, 132.8, 133.0, 134.6, 134.7, 134.9, 135.9, 136.3, 136.4, 48 ACS Paragon Plus Environment

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136.5, 136.86, 136.91, 137.0, 137.1, 137.6, 138.0, 139.2, 160.0, 164.9, 165.0, 165.6, 165.9, 167.2, 167.4, 167.7.

Supporting Information 1

H and 13C NMR spectra and additional results for CD, UV-vis, fluorescence spectra, DLS profiles,

and DOSY experiment.

Acknowledgement We thank Mr. Shin-ichiro Yoshida (Tohoku University) for performing the DOSY data collection. This work was financially supported by a Grant-in-Aid for Scientific Research (No. 15H00981) from the Japan Society for the Promotion of Science (JSPS) and the Takahashi Industrial and Economic Research Foundation.

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Pendant-Type Helicene Oligomers with p-Phenylene

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