Copper-Catalyzed Perfluoroalkylation of Allyl Phosphates with Stable

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Copper-Catalyzed Perfluoroalkylation of Allyl Phosphates with Stable Perfluoroalkylzinc Reagents Lihua Liu, Xifei Bao, Hua Xiao, Junlan Li, Feifan Ye, Chaoqin Wang, Qinhua Cai, and Shilu Fan J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02432 • Publication Date (Web): 07 Dec 2018 Downloaded from http://pubs.acs.org on December 7, 2018

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The Journal of Organic Chemistry

Copper-Catalyzed Perfluoroalkylation of Allyl Phosphates with Stable Perfluoroalkylzinc Reagents

Lihua Liu,+,ǁ Xifei Bao,+,† Hua Xiao,ǁ Junlan Li,† Feifan Ye,† Chaoqin Wang,† Qinhua Cai,† and Shilu Fan*,†,‡,§ †

School of Chemistry and Chemical Engineering, Hefei University of Technology, 193 Tunxi Road,

Anhui, 230000, People's Republic of China ‡

Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese

Academy of Sciences §

Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering

ǁ

School of Biological and Medical Engineering, Hefei University of Technology, 193 Tunxi Road,

Anhui, 230000, People's Republic of China +

These authors contributed equally.

[email protected]

TOC

Keywords: copper, cross-coupling, perfluoroalkylation, allyl, selectivity

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ABSTRACT. A general and practical method for copper-catalyzed cross-coupling of allyl phosphates with stable perfluoroalkylzinc reagents has been developed. The reaction proceeds under mild reaction conditions with high efficiency, good functional group tolerance, high regio- and stereoselectivities, and provides a general, straightforward and useful access to allyl-perfluoroalkyl compounds. Preliminary mechanistic studies reveal that the allyl copper intermediate may be involved in the catalytic cycle.

Transition metal-catalyzed allylation reaction is one of the most frequently employed transformations in organic synthesis owing to the presence of allyl moieties in many biologically active compounds.1 Moreover, the synthetical usefulness of allylic motifs is ascribed to the fact that the carbon–carbon double bond can transfer to a variety of structures after simple manipulations.2 The scenery is clearly dominated by Pd catalysts, but during the last decade a range of other metals, especially late transition metals (Ru, Rh, Ir, et al.),3 made their way into the limelight. Inspired by the earlier studies on coppercatalyzed perfluoroalkylation of aryl boronic acids4 and aromatic halides,5 we hypothesized that the copper-catalyzed cross-coupling of allylic electrophilies with stable perfluoroalkylating reagents may be possible, and would benefit the preparation of allylated perfluoroalkyl compounds. Although TsujiTrost reaction involving addition of a nucleophile to (-allyl)palladium intermediate offers a powerful tool for preparation of allyl-substituted compounds, the reaction of highly electron-deficient perfluoroalkyl groups through the present strategy has rarely been studied.6 Consequently, developing new transition-metal-catalyzed allylative cross-coupling reactions for widespread applications is still highly desirable. Organic compounds bearing a perfluoroalkyl group (RF) have been adopted in a wide range of applications such as agrochemicals, pharmaceuticals, and materials because of the unique properties of the fluorine atom.7 Over the past decade, considerable effort has been dedicated to the efficient introduction of perfluoroalkyl groups.8 The generation of allyl-RF bonds, however, remains synthetically challenging, particularly via transition metal catalysis. Matsubara described Pd-catalyzed coupling of allyl and alkenylstannanes with perfluoroalkyl iodides,9 whereas Cu-mediated nucleophilic 2 ACS Paragon Plus Environment

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trifluoromethylation of allyl halides were also reported.10 In 2011, a copper-catalyzed Heck-type trifluoromethylation of terminal alkenes through allylic C-H bond activation was described by the group of Liu and Fu.11 Furthermore, Wang,12 Buchwald,13 Qing,14 and Sodeoka15 independently described the copper-catalyzed

trifluoromethylation

of

alkenes

using

elecrophilic-

or

nucleophilic

trifluoromethylating reagents and involving the addition of CF3 radical to alkenes. Very recently, Sodeoka and co-workers realized a perfluoroalkylation of unactivated alkenes with acid anhydrides as the perfluoroalkyl source.16 Most of the above reactions are focus on radical trifluoromethylation reaction, the perfluoroalkylation (C2F5, C3F7, C4F9, C6F13 et al.) reaction via allyl-M-RF intermediate reductive elimination remains challenging so far17. Moreover, it is hard to find an efficient perfluoroalkylating reagent. Only CF3SiR3, C2F5SiR3, C3F7SiR3, Togni, and Umemoto reagents are commercially available, yet very expensive. As the cheap and safe perfluoroalkyl source, perfluoroalkyl halides18 and perfluoroalkanesulfonyl halides19 are prone to generate perfluoroalkyl radicals. In 2011, Daugulis and co-workers synthesized (RF)2Zn from 1H-perfluoroalkane by deprotonative metalation with TMP2Zn and used it in copper-catalyzed perfluoroalkylation of aromatic iodides.20 These reagents are confined to C(sp2)–RF bonds4-5 generation until now, which creates the interesting challenge of establishing new transition-metal-catalyzed perfluoroalkylation reactions to form C(sp3)–RF bonds (Scheme 1). Herein, we report a practical example of copper-catalyzed perfluoroalkylation of allyl phosphates with a broad range of substrates in moderate to high yields and with moderate to high stereo- and regioselectivities.



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Scheme 1. Representative approaches to preparation of allyl-RF compounds. Initially, allyl phosphate (E)-1a and bis(perfluoroalkyl)zinc reagent 2c were chosen as model substrate to investigate this reaction (Table 1). To our delight, the treatment of (E)-1a and 2c in the presence of a catalytic amount of CuI/phen in the 1, 4-dioxane at 100 oC afforded 3ac in a 77% isolated yield with high regio- and stereoselectivity (linear/branched >99:1, E/Z =18:1; Table 1, entry 1). Encouraged by this result, a series of copper catalyst, such as CuSCN, Cu(OAc)2, Cu(acac)2, employed in these reactions were examined (Table 1, entries 2–4), and a higher yield was observed only with Cu(acac)2 (Table 1, entry 4, 80% yield). The nature of the solvent and ligand was critical to the reaction efficiency, and the use of ether solvent and L2 (4,7-diphenyl-1,10-phenanthroline) was found to provide the most efficient reaction, providing 3ac in 85% isolated yield (Table 1, entry 9). The control experiments revealed that a copper intermediate is involved in the reaction catalytic cycle (Table 1, entry 10). To our surprise, 52% isolated yield was obtained without ligand (Table 1, entry 11). DMPU dissociated from 2c, as a ligand, chelates with copper centre for stabilizing the catalytic intermediate.5b An attempt to decrease the loading of Cu(acac)2 to 5 mol% resulted in the yield dropping to 71% (Table 1, entry 12). Meanwhile, the choice of leaving group on the allyl substrate was crucial, the reaction of the corresponding acetate, halides or carbonate instead of the phosphate resulted in low yields or no formation of the desired product. Table 1. Table 1. Representative results for optimization of copper-catalyzed perfluoroalkylation of phosphate (E)-1aa

Entry

Cu source

Ligand

Solvent

Yield(%)b

1

CuI

phen

Dioxane

77

2

CuSCN

phen

Dioxane

53

3

Cu(OAc)2

phen

Dioxane

64 4

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4

Cu(acac)2

phen

Dioxane

80

5

Cu(acac)2

phen

THF

48

6

Cu(acac)2

phen

DME

46

7

Cu(acac)2

phen

Diglyme

47

8

Cu(acac)2

L1

Dioxane

74

9

Cu(acac)2

L2

Dioxane

85

10

–

L2

Dioxane

NR

11

Cu(acac)2

–

Dioxane

52

12

Cu(acac)2

L2

Dioxane

71c

a

Reaction conditions (unless otherwise specified): (E)-1a (0.2 mmol, 1.0 equiv), 2c (1.0 equiv), solvent (2 mL). b All the yields were isolated yield. c 5 mol% CuI and 5 mol% phen were used. phen = 1,10phenanthroline, L1 = 3,4,7,8-tetramethyl-1,10-phenanthroline, L2 =4,7-diphenyl-1,10-phenanthroline. NR = no reaction. Under the optimum reaction conditions, a variety of allylated perfluoroalkyl compounds were generated by the present method and good to high yields and regioselectivities were obtained (Scheme 2). Generally, alkyl-substituted allyl phosphates bearing functional groups apart from the carbon-carbon double bond coupled with 2c effectively (3a-f). It is noteworthy that many versatile functional groups, including base- and nucleophile-sensitive moieties, such as silyl ether, acetate, phosphate, halide, and hydroxyl, showed good tolerance toward the reaction conditions, providing opportunities for further functionalization without the need of protection/deprotection sequences. Importantly, product 3d also revealed an excellent chemical selectivity at allyl phosphate over alkyl phosphate. However, it should be mentioned that the reaction efficiency highly depends on the nature of steric hindrance on substrates. Substrates with the bulky substituted groups near the reaction centre (carbon-carbon double bond) gave the desired products with a moderate yields (35-64%) and excellent regio- and stereoselectivities (3g-k). Furthermore, aromatic allyl phosphates were also suitable substrates, and reasonable yields with high stereoselectivities were still generated (3l-o). Notably, no branched product was observed with cinnamyl phosphates under this catalytic system.



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Scheme 2. Copper-catalyzed perfluoroalkylation of allyl phosphates (E)-1a

a

Reaction conditions (unless otherwise specified): (E)-1 (0.3 mmol, 1.0 equiv), 2c (1.0 equiv), Cu(acac)2 (10 mol%), L2 (10 mol%), dioxane (2 mL), 100 oC, 12h. b The yields are of isolated products and the E/Z ratios were determined by 1H NMR spectroscopy. In all cases the linear and branched ratios were > 99:1. c 2.0 equiv 2c was used. L2 = 4,7-diphenyl-1,10-phenanthroline. To prove the generality of these observations and evaluate the scope and limitations of this protocol, a wide range of other perfluoroalkylzinc reagents 2 were employed in optimized reaction conditions (Scheme 3). In a similar manner to the perfluorobuthylation, allyl phosphates with versatile substituents gave moderate-to-good yields (49-77%), and high regio- and steroselectivities (4a-6d). It should be noted that yields and selectivities are interrelated with the length of RF. The reaction with C2, C3 homologous perfluoroalkylzinc reagents afforded desired products with higher yields and selectivities 6 ACS Paragon Plus Environment

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than that of C6 perfluoroalkylzinc reagents. In the catalytic process, the rate of transmetallation of perfluoroalkyl group to copper centre from Zn(RF)2(DMPU)2 decreases due to the growing length of RF, which readily causes Schlenk equilibrium to Zn(RF)2(DMPU)2 and ZnX2.21 For allyl phosphates with steric hindrance such as 1g, 1l and 1m, the desired products were obtained with moderate yields and excellent regio- and stereoselectivities (4g-5n), thus suggestion that the steric effect still plays an important role in the yield and selectivity. Scheme 3. Copper-catalyzed perfluoroalkylation of allyl phosphates (E)-1 with various perfluoroalkylzinc reagents 2a O OP(OEt)2

R

(E)-1

CH3(CH2)10

+

Cu(acac)2 (10 mol%) L2 (10 mol%)

o 2a, RF=C2F5; 2b, RF=C3F7; Dioxane, 100 C, 12h 2d, RF=C6F13

RF

RF=C2F5, 4a, 77% (18:1) RF=C3F7, 5a, 70% (23:1) RF=C6F13, 6a, 61% (7:1) Me

(DMPU)2Zn(RF)2

RF

RF

TBSOCH2(CH2)10 RF=C3F7, 5b, 67% (17:1) RF=C6F13, 6b, 52% (10:1)

RF=C2F5, 4g, 59% (＞99:1)c RF=C3F7, 5g, 60% (＞99:1)c

RF 4-6

(EtO)2(O)PO(CH2)11

RF

RF=C3F7, 5d, 64% (25:1) RF=C6F13, 6d, 49% (20:1)

RF

RF

Me

R

tBu RF=C2F5, 4l, 45% (＞99:1) RF=C3F7, 5l, 42% (＞99:1)

RF=C2F5, 4n, 47% (＞99:1) RF=C3F7, 5n, 44% (＞99:1)

a

Reaction conditions (unless otherwise specified): (E)-1 (0.3 mmol, 1.0 equiv), 2 (1.0 equiv), Cu(acac)2 (10 mol%), L2 (10 mol%), dioxane (2 mL), 100 oC, 12 h. b The yields are of isolated products and the E/Z ratios were determined by 1H NMR spectroscopy. In all cases the linear and branched ratios were generally > 99:1. c 2.0 equiv 2 was used. L2 =4,7-diphenyl-1,10-phenanthroline. To investigate the regio- and stereoselectivity of the reaction, the branched allyl phosphate 7 and 8, Z-allyl phosphates (Z)-1p and (Z)-1l were also subjected to the standard reaction conditions (Scheme 4). In general, under the above conditions these substrates give the linear products predominantly as an (E/Z)-mixture, with the (E)-products as the major one, thus indicating that a-ally copper intermediate is involved in the catalytic process [Eq. (1)]. It should be noted that the stereochemical information of 7 ACS Paragon Plus Environment


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(Z)-substrates was partially retained which implies that the (E/Z)-mixtures were generated via two simultaneous pathways at least [Eq. (2)]. Scheme 4. Copper-catalyzed perfluoroalkylation of branched allyl phosphate 4, 5, and linear phosphates (Z)-1 with perfluoroalkylzinc reagents 2a OP(O)(OEt)2

+

(DMPU)2Zn(RF)2

R

O OP(OEt)2

(Z)-1l, R=Ph (Z)-1p, R=(H2C)10CH3

+

(DMPU)2Zn(RF)2

R

RF

(1)

RF=C2F5, 4a 77% (E/Z=13:1) RF=C2F5, 4l, 42%(E/Z＞99:1) RF=C3F7, 5a, 81% (E/Z=9:1) RF=C3F7, 5l, 42%(E/Z＞99:1) RF=C4F9, 3a, 69% (E/Z=13:1) RF=C6F13, 6a, 59% (E/Z=5:1)

2

7, R=(H2C)10CH3 8, R=Ph

R

standard conditon

standard conditon

2

R

RF

(2)

RF=C3F7, 5l, 41% (E/Z＞99:1) RF=C4F9, 3l, 42% (E/Z＞99:1) RF=C4F9, 3p, 88% (E/Z=3:1) RF=C6F13, 6p, 71% (E/Z=10:7)

a

Standard condition: allyl phosphate (0.3 mmol, 1.0 equiv), 2 (1.0 equiv), Cu(acac)2 (10 mol%), L2 (10 mol%), dioxane (2 mL), 100 oC, 12 h. b The yields are of isolated products and the E/Z ratios were determined by 1H NMR spectroscopy. L2 =4,7-diphenyl-1,10-phenanthroline. Although the exact mechanism of the reaction is still not clear, on the basis of the results reported by others,5-6 a plausible mechanism is proposed and shown in Scheme 5. The sequence begins with formation of copper catalyst I by in situ generation. Then, copper intermediate II was generation by transmetalation of copper catalyst with zinc reagent 2. Subsequently, oxidative addition of (Z)- or (E)-1 with RFCu(I)Ln (II) would provide the key copper species (Z)- or (E)-III, respectively. Finally, the reductive elimination would lead to the desired allylated product (Z)- or (E)-3, and regenerate the Cu(I)Ln species (path A). Alternatively, a reversible pathway conduct to form allyl copper complex IV from III by rapid-conversion (path B), which would give the (E)-3 as the major product, thus resulting in stereochemical inversion in (Z)-substrates. Scheme 5. Proposed reaction mechanism


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CONCLUSION In conclusion, we have demonstrated an efficient copper catalyst system for the perfluoroalkylation of phosphates with good-to-excellent yields and high regio- and stereoselectivities, which represents a useful, concise, and operationally simple method to the preparation of allyl-RF products. A preliminary study suggests that the reaction mechanism is complex and two main pathways leading to the desired allyl-RF products may be operating. Further studies to expand the substrate scope and their applications are now in progress in our laboratory.

EXPERIMENTAL SECTION General information: 1H NMR and

13

C NMR spectra were recorded on a Bruker 600 MHz

spectrometer in CDCl3. Data for 1H NMR are reported as follows: chemical shift (ppm, scale), multiplicity, coupling constant (Hz), and integration. Data for

13

C NMR are reported in terms of

chemical shift (ppm, scale), multiplicity, and coupling constant (Hz). High resolution mass spectrometry (HRMS) analysis was performed by the analytical facility at the University of Science and Technology of China. 9 ACS Paragon Plus Environment


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Materials: All reagents were used as received from commercial sources, unless specified otherwise, or prepared as described in the literature. All reagents were weighed and handled in air, and refilled with an inert atmosphere of N2 at room temperature. DMF, DMSO, DMPU, NMP, and DCE were distilled under reduced pressure from CaH2. Toluene, 1,4-Dioxane, THF, Diglyme, and DME were distilled from sodium and benzophenone immediately before use. Preparation of compounds (E)-(1a, 1g, 1h, 1i , 1j, 1l, 1m, 1n, 1o). To a stirred solution of ethyl 2-(diethoxyphosphoryl)acetate (1.97 g, 8.8 mmol) in anhydrous THF (20 mL) was added MeMgBr (2.7 mL, 8 mmol) at room temperature and the mixture was stirred for 15 min. aldehyde (848 mg, 8 mol) dissolved in THF (5 mL) was added at room temperature and stirred for 4 h under reflux. After cooled to room temperature, the reaction was quenched with distilled water and the aqueous phase was extracted with EA (2 × 30 mL). The combined organic layers were washed with brine, dried (Na2SO4), and concentrated in vacuo to give the crude product which was used in the next step. The crude product was dissolved in DCM (15 mL), DIBAL-H (10.7 ml, 16 mmol) was added at RT. and the mixture was stirred for 2 h (TLC monitoring). The mixture was quenched with sat. NH4Cl solution and the aqueous phase was extracted with EA (2 × 30 mL). The combined organic layers were washed with brine, dried (Na2SO4), and concentrated in vacuo to give the allyl alcohol which was used in the next step. The DMAP (244.4 mg, 2.0 mmol) were placed in a 20 mL two-necked reaction flask at 0 oC temperature, which was filled with nitrogen by using the standard Schlenk technique. DCM (10 mL) was then added to the flask, allyl alcohol (10 mmol) dissolved in DCM (5 mL) was added. Finally, Et3N (1.66 mL, 12 mmol) and diethyl phosphorochloridate (1.71 mL, 12 mmol) was added dropwise. The solution was stirred at 0 oC temperature for 4 h, and diluted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography to provide pure product. 10 ACS Paragon Plus Environment

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(E)-diethyl tetradec-2-en-1-yl phosphate ((E)-1a). The product (2.10 g, 62% yield) as a colourless oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3)  5.77 (dt, J = 15.0 Hz, J = 6.6 Hz, 1 H), 5.56 (dt, J = 15.0 Hz, J = 6.6 Hz, 1 H), 4.44 (t, J = 8.4 Hz, 2 H), 4.07 (m, 4 H), 2.01 (m, 2 H), 1.31-1.22 (m, 24 H), 0.84 (m, 3 H).

13

C NMR (150.8 MHz,

CDCl3)  136.6, 124.2 (d, J = 6.6 Hz), 68.2 (d, J = 5.7 Hz), 63.5 (d, J = 5.7 Hz), 32.1, 31.9, 29.6, 29.5, 29.4, 29.3, 29.2, 29.1, 28.8, 22.6, 16.1 (d, J = 6.7 Hz), 14.1. IR (thin film): max 2925, 1269, 1033 cm-1. LRMS (EI): m/z (%) 348(M+), 207, 84(100). HRMS (APCI-LTQ Orbitrap) m/z: [M+H]+ Calculated for C18H38O4P: 349.2502; Found: 349.2496. (E)-diethyl (4-methylhept-2-en-1-yl) phosphate ((E)-1g). The product (1.98 g, 75% yield) as a colourless oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3) 5.57 (dd, J = 15.0 Hz, J = 6.6 Hz, 1 H), 5.77 (dt, J = 15.6 Hz, J = 6.6 Hz, 1 H), 4.39 (m, 2 H), 4.01 (m, 4 H), 2.07 (m, 1 H), 1.25 -1.17 (m, 10 H), 0.89-0.77 (m, 6 H). 13C NMR (150.8 MHz, CDCl3)  142.1, 122.5 (d, J = 6.5 Hz), 68.2 (d, J = 5.7 Hz), 63.5 (d, J = 5.7 Hz), 38.7, 36.0, 20.2, 20.0, 16.0 (d, J = 6.7 Hz), 14.0. IR (thin film): max 2962, 1267, 1035 cm-1. LRMS (EI): m/z (%) 264(M+), 95, 67(100). HRMS (APCI-LTQ Orbitrap ) m/z: [M+H]+ Calculated for C12H26O4P: 265.1563; Found: 265.1565. (E)-3-cyclohexylallyl diethyl phosphate ((E)-1h). The product (1.52 g, 55% yield) as a colourless oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3) 5.70 (dd, J = 15.6 Hz, J = 6.6 Hz, 1 H), 5.51 (dt, J = 15.6 Hz, J = 6.6 Hz, 1 H), 4.44 (t, J = 7.2 Hz, 2 H), 4.08 (m, 4 H), 1.95 (m, 1 H), 1.60-1.69 (m, 5 H), 1.03-1.31 (m, 11 H). This compound is known.22 (E)-diethyl (4-phenylbut-2-en-1-yl) phosphate ((E)-1i). The product (1.62 g, 57% yield) as a colourless oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3)  7.12 (t, J = 7.2 Hz, 2 H), 7.04 (d, J = 7.2Hz, 1 H), 7.01 (d, J = 7.8 Hz, 2 H), 11 ACS Paragon Plus Environment


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5.80 (dt, J = 15.0 Hz, J = 6.6 Hz, 1 H), 5.50 (dt, J = 15.6 Hz, J = 6.6 Hz, 1 H), 4.36 (t, J = 7.8 Hz, 2 H), 3.93 (m,4 H), 3.32 (d, J = 6.6 Hz, 2 H), 1.16 (m, 6 H). This compound is known.23 (E)-diethyl (5-phenylpent-2-en-1-yl) phosphate ((E)-1j). The product (1.82 g, 61% yield) as a colourless oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3)  7.26 (t, J = 6.0 Hz, 2 H), 7.15 (m, 3 H), 5.81 (dt, J = 15.6 Hz, J = 6.6 Hz, 1 H), 5.61(dt, J = 15.0 Hz, J = 6.6 Hz, 1 H), 4.44 (t, J = 12.0 Hz, 2 H), 4.08 (m, 4 H), 2.68 (t, J = 6.0 Hz, 2 H), 2.37 (q, J = 7.8 Hz, 2 H), 1.31 (m, 6 H). 13C NMR (150.8 MHz, CDCl3)  141.4, 135.2, 128.4, 128.3 (d, J = 4.8 Hz), 125.9, 125.0 (d, J = 6.6 Hz), 68.0 (d, J = 6.7 Hz), 63.6 (d, J = 5.9 Hz), 35.2, 33.9, 16.1 (d, J = 6.7 Hz). HRMS (APCI-LTQ Orbitrap ) m/z: [M+H]+ Calculated for C15H24O4P: 299.1047; Found: 299.1045. This compound is known.22 Cinnamyl diethyl phosphate ((E)-1l). The product (2.61 g, 90% yield) as a colourless oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3)  7.37 (d, J = 7.2 Hz, 2 H), 7.30 (t, J = 7.2 Hz, 2 H), 7.24 (t, J = 7.2 Hz, 1 H), 6.66 (d, J = 15.6 Hz, 1 H), 6.30 (dt, J = 16.2 Hz, J = 6.0 Hz, 1 H), 4.67 (m, 2 H), 4.11 (m, 4 H), 1.32 (t, J = 17.8 Hz, 6 H). This compound is known.22 (E)-diethyl (3-(p-tolyl)allyl) phosphate ((E)-1m). The product (2.32 g, 82% yield) as a colourless oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3) 7.29 (d, 2H, J = 8.2 Hz), 7.13 (d, 2H, J = 8.2 Hz), 6.45 (d, 1H, J = 15.9 Hz), 6.25 (dt, 1H, J = 6.4, 15.9 Hz), 4.69 (dt, 2H, J = 1.2, 6.4 Hz), 4.13 (dq, 4H, J = 7.0, 7.0 Hz), 2.34 (s 3H), 1.34 (t, 6H, J = 7.0). This compound is known.24 (E)-3-(4-(tert-butyl)phenyl)allyl diethyl phosphate ((E)-1n). The product (2.51 g, 77% yield) as a colourless oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3)  7.35 (d, J = 8.4 Hz, 2 H), 7.32 (d, J = 8.4 Hz, 2 H), 6.65 (d, J = 16.0 Hz, 1 H), 6.26 (dt, J = 16.0 Hz, J = 6.6 Hz, 1 H), 4.68 (t, J = 7.2 Hz, 2 H), 4.12 (m, 4 H), 1.34-1.28 (m, 15 H). 12 ACS Paragon Plus Environment

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13


C NMR (150.8 MHz, CDCl3)  151.3, 133.8, 133.2, 127.8, 126.4, 125.5, 122.7 (d, J = 6.5 Hz), 68.1 (d,

J = 5.7 Hz), 63.7 (d, J = 5.7 Hz), 31.2, 16.1 (d, J = 6.8 Hz), 14.0. IR (thin film): max 2965, 1271, 1035 cm-1. LRMS (EI): m/z (%) 326(M+), 207(100). HRMS (APCI-LTQ Orbitrap ) m/z: [M+H]+ Calculated for C17H28O4P: 327.1720; Found:327.1721. (E)-diethyl (3-(3-methoxyphenyl)allyl) phosphate (1o). The product (2.16 g, 72% yield) as a colourless oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3)  7.25 (m, 2 H), 6.96 (m, 2 H), 6.82 (d, J = 7.8 Hz, 1 H), 6.65 (d, J = 16.2 Hz, 1 H), 6.30 (dt, J = 15.6 Hz, J = 6.0 Hz, 1 H), 4.70 (t, J = 7.2 Hz, 2 H), 4.13 (m, 4 H), 3.81 (s, 3 H), 1.32 (m, 6 H). This compound is known.22 Preparation of compound (E)-1k. Ethyl 2-(diethoxyphosphoryl)acetate (1.35 g, 6.0 mmol) was slowly added to a solution of NaH (60%, 240 mg, 6.0 mmol) in THF (20 mL) at 0 oC. After 1 h of stirring, a solution of undecan-2-one (951 mg, 5.0 mmol) in THF (5 mL) was added dropwise to the solution of olefinating agent, and the resulting mixture was allowed to slowly warm to RT. After 12 h, H2O (20 mL) was added, and diluted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography to provide pure ethyl ethyl (E)-3-methyldodec-2-enoate (780 mg, 65%) as a pale yellow oil. The (E)-3-methyldodec-2-enoate (780 mg, 3.25 mmol) was dissolved in DCM (15 mL), DIBAL-H (4.4 mL, 6.5 mmol) was added at RT. and the mixture was stirred for 2 h (TLC monitoring). The mixture was quenched with sat. NH4Cl solution and the aqueous phase was extracted with EA (2 × 30 mL). The combined organic layers were washed with brine, dried (Na2SO4), and concentrated in vacuo to give the (E)-3-methyldodec-2-en-1-ol which was used in the next step. The DMAP (99 mg, 0.81 mmol) were placed in a 20 mL two-necked reaction flask at 0 oC temperature, which was filled with nitrogen by using the standard Schlenk technique. DCM (10 mL) was then added 13 ACS Paragon Plus Environment


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to the flask, (E)-3-methyldodec-2-en-1-ol dissolved in DCM (5 mL) was added. Finally, Et3N (675.8 ul, 4.88 mmol) and diethyl phosphorochloridate (670.1 mL, 4.88 mmol) was added dropwise. The solution was stirred at 0 oC temperature for 4 h, and diluted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1) to provide pure (E)-1k (750.0 mg, 69% yield) as a clear, pale yellow oil. 1H NMR (600 MHz, CDCl3) 5.80 (m, 1 H), 5.27 (d, J = 17.4 Hz, 1 H), 5.17 (d, J = 10.80 Hz, 1 H), 4.71 (m, 1 H), 4.05 (m, 4 H), 1.73-1.55 (m, 2 H), 1.33-1.22 (m, 24 H), 0.85 (t, J = 6.6 Hz, 2 H). 13C NMR (150.8 MHz, CDCl3)  143.0, 118.6 (d, J = 6.6 Hz), 64.1 (d, J = 5.7 Hz), 63.5 (d, J = 5.9 Hz), 39.5, 31.8, 29.5, 29.4, 29.3, 29.2, 27.5, 22.6, 16.3, 16.1 (d, J = 6.6 Hz), 14.1. IR (thin film): max 2927, 1267, 1040 cm-1. LRMS (EI): m/z (%) 334(M+), 281, 207(100). HRMS (APCI-LTQ Orbitrap ) m/z: [M+H]+ Calculated for C17H36O4P: 335.2346; Found: 335.2344. Preparation of compound B4. To a suspension of NaH (60%, 1.0 g, 25.0 mmol) and decane-1,10-diol (B1) (4.4 g, 25.0 mmol) in THF (30 mL) was slowly added TBSCl (3.8 g, 25.0 mmol) in THF (25 mL), and the resulting mixture was stirred at room temperature for 2 h. The mixture was quenched with sat. aq. NaHCO3 and was extracted with EA (2 × 30 mL). The organic layer was dried over Na2SO4 and evaporated. The residue was purified with column chromatography (Petroleum ether / Ethyl ether =20:1) to afford alcohol (B2) (5.76 g, 80%) as a pale yellow oil. To a stirred solution of oxalyl chloride (2.54 mL, 30 mmol) in anhydrous DCM (30 mL) at –78 oC was added DMSO (4.25 mL, 60.0 mmol) over 20 min and the mixture was stirred for an additional 15 min. Alcohol B2 (5.77 mg, 20 mmol) dissolved in DCM (10 mL) was added and the mixture was stirred for 30 min. Et3N (13.86 mL, 100 mmol) was added dropwise and the mixture was stirred at r.t. for 1 h (TLC monitoring). The mixture was quenched with water and the aqueous phase was extracted with EA (2 × 20 mL). The combined organic layers were washed with brine, dried (Na2SO4), and concentrated in vacuo to give the aldehyde (B3) which was used in the next step. 14 ACS Paragon Plus Environment

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To a stirred solution of ethyl 2-(diethoxyphosphoryl)acetate (4.93 g, 22.0 mmol) in anhydrous THF (30 mL) was added MeMgBr（2.7 mL, 8 mmol）at room temperature and the mixture was stirred for 15 min. Aldehyde B3 dissolved in THF (100 mL) was added at room temperature and stirred for 4 h under reflux. After cooled to room temperature, the reaction was quenched with distilled water and the aqueous phase was extracted with EA (2 × 30 mL). The combined organic layers were washed with brine, dried (Na2SO4), and the residue was purified with column chromatography (Petroleum ether / Ethyl ether = 20:1) to afford ethyl (B4) (6.21 g, 86%) as a pale yellow oil. Preparation of compound (E)-1b To a stirred solution of ethyl (B4) (3.57 g, 10 mmol) in anhydrous DCM (25 mL) at –78 oC was added 1.5 M DIBAL-H in toluene (13.4 mL, 20.0 mmol) slowly over 15 min. The mixture was stirred at this temperature for 2 h, cooled to 0 oC, and quenched with sat. Sodium potassium tartrate and the mixture stirred for 2 h. The mixture was passed through a bed of Celite. The filtrate was extracted with EA (2 × 20 mL) and the combined organic extracts were washed with brine, dried (Na2SO4), and concentrated in vacuo to give the alcohol (B6) which was used in the next step. The DMAP (305.4 mg, 2.5 mmol) were placed in a 50 mL two-necked reaction flask at 0 °C temperature, which was filled with nitrogen by using the standard Schlenk technique. DCM (25 mL) was then added to the flask, alcohol (B6) dissolved in DCM (10 mL) was added. Finally, Et3N (2.08 mL, 15 mmol) and diethyl phosphorochloridate (2.14 mL, 15 mmol) was added dropwise. The solution was stirred at 0 °C temperature for 4 h, and diluted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1) to provide (E)-1b (3.65 g, 81% yield) as a clear, pale yellow oil. 1H NMR (600 MHz, CDCl3) 5.74 (dt, J = 15.0 Hz, J = 6.6 Hz, 1 H), 5.54 (dt, J = 15.0 Hz, J = 6.6 Hz, 1 H), 4.42 (t, J = 7.2 Hz, 2 H), 4.05 (m, 4 H), 3.54 (t, J = 6.6 Hz, 2 H), 2.00 (q, J = 7.2 Hz, 2 H), 1.44 (m, 2 H), 1.29 (m, 18 H), 0.84 (d, J = 1.2 Hz, 9 H), -0.01 (d, J = 1.8 Hz, 6 H). 13C NMR (150.8 MHz, CDCl3)  136.6, 124.3 (d, J = 6.5 Hz), 68.1 (d, J = 5.6 Hz), 63.6 (d, J = 5.9 Hz), 63.3, 32.8, 32.1, 29.5, 29.4, 29.3, 29.1, 28.8, 15 ACS Paragon Plus Environment


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25.9, 25.7, 18.3, 16.1 (d, J = 6.6 Hz), -5.3. IR (thin film): max 2931, 2860, 1036 cm-1. LRMS (EI): m/z (%) 464(M+), 281, 207(100). HRMS (APCI-LTQ Orbitrap ) m/z: [M+H]+ Calculated for C23H50O5PSi: 465.3160; Found: 465.3158. Preparation of compound (E)-1c To a stirred solution of acetic anhydride (216 uL, 2.1 mmol), DMAP (122.2 mg, 1.0 mmol) in anhydrous DCM (5 mL) at RT was added (1f) (168.1 mg, 0.5 mmol) slowly. The mixture was stirred at room temperature until starting material is consumed. The reaction was poured into water (10 mL), and the mixture was stirred vigorously for 30 min. The aqueous phase was extracted with EA (2×20 mL). The combined organic phases were washed with 1 M aq HCl (15 ml), saturated aq NaHCO3 (20 mL), water (20 mL) and brine (2 mL), and dried over anhydrous Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1) to provide pure (E)-1c (159 mg, 89% yield) as a clear, pale yellow oil. 1H NMR (600 MHz, CDCl3) 5.70 (dt, J = 15.0 Hz, J = 6.6 Hz, 1 H), 5.55 (dt, J = 15.0 Hz, J = 6.0 Hz, 1 H), 4.39 (t, J = 7.2 Hz, 2 H), 4.02 (m, 4 H), 3.95 (t, J = 6.6 Hz, 2 H), 1.98-1.95 (m, 5 H), 1.52 (m, 2 H), 1.17-1.29 (m, 18 H). 13C NMR (150.8 MHz, CDCl3)  171.2, 136.5, 124.2 (d, J = 6.6 Hz), 68.2 (d, J = 5.7 Hz), 64.6, 63.6 (d, J = 5.9 Hz), 32.1, 29.4, 29.3, 29.1, 29.0, 28.7, 28.5, 25.8, 21.0, 16.0 (d, J = 6.6 Hz). IR (thin film): max 2931, 1742, 1036 cm-1. LRMS (EI): m/z (%) 378(M+), 281, 207(100), 84. HRMS (APCI-LTQ Orbitrap ) m/z: [M+H]+ Calculated for C18H36O6P: 379.2244; Found: 379.2239. Preparation of compound (E)-1d To a stirred solution of ethyl (B4) (713 mg, 2 mmol) in anhydrous DCM (10 mL) at 40 °C was added 1.5 M DIBAL-H in toluene (2.8 mL, 4.0 mmol) instantly. The mixture was stirred at this temperature for 2 h, cooled to RT, and quenched with sat. Sodium potassium tartrate and the mixture stirred for 2 h. The mixture was passed through a bed of Celite. The filtrate was extracted with EA (2 × 20 mL) and the


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combined organic extracts were washed with brine, dried (Na2SO4), and concentrated in vacuo to give the alcohol (B5) which was used in the next step. The DMAP (122.2 mg, 0.81 mmol) were placed in a 20 mL two-necked reaction flask at 0 oC temperature, which was filled with nitrogen by using the standard Schlenk technique. DCM (10 mL) was then added to the flask, alcohol (B5) dissolved in DCM (5 mL) was added. Finally, Et3N (0.83 mL, 6.0 mmol) and diethyl phosphorochloridate (0.86 mL, 6 mmol) was added dropwise. The solution was stirred at 0 °C temperature for 4 h, and diluted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 1:1) to provide (E)-1d (793.4 mg, 84% yield) as a clear, pale yellow oil. 1H NMR (600 MHz, CDCl3) 5.71 (dt, J = 15.6 Hz, J = 6.6 Hz, 1 H), 5.51 (dt, J = 15.6 Hz, J = 6.6 Hz, 1 H), 4.39 (t, J = 7.2 Hz, 2 H), 4.18 (m, 2 H), 4.03 (m, 8 H), 3.95 (q, J = 6.6 Hz, 2 H), 1.97 (q, J = 7.2 Hz, 2 H), 1.59 (m, 2 H), 1.20-1.32 (m, 22 H). 13C NMR (150.8 MHz, CDCl3)  136.5, 124.2 (d, J = 6.5 Hz), 68.1 (d, J = 5.6 Hz), 67.6 (d, J = 6.0 Hz), 63.6 (t, J = 5.1 Hz), 32.1, 30.2, 30.1, 29.4, 29.3, 29.1, 29.0, 28.7, 25.4, 16.1 (d, J = 6.6 Hz), 16.0 (d, J = 6.8 Hz). IR (thin film): max 2931, 1276, 1037 cm-1. LRMS (EI): m/z (%) 472(M+), 281, 207(100). HRMS (APCI-LTQ Orbitrap ) m/z: [M+H]+ Calculated for C20H43O8P2: 473.2428; Found: 473.2423. Preparation of compound (E)-1e To a flask containing a stirring mixture of DDQ (136.2 mg, 1.2 mmol) and PPh3 (157.4 mg，1.2 mmol) in dry DCM (5 mL), was added TBAB (199.5 mg, 1.2 mmol) at room temperature. (1f) (168.16 mg, 0.5 mmol) was then added to this mixture. The yellow color of the reaction mixture was immediately changed to deep red. GC analysis showed the immediate completion of the reaction. The solvent diluted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 7:3) to provide pure (E)-1e (181.7 mg, 91% yield) as a clear, pale yellow oil. 1H NMR (600 MHz, CDCl3) 5.74 (dt, J = 15.0 Hz, J = 6.6 Hz, 1 H), 5.54 (dt, J = 15.6 Hz, J = 6.0 Hz, 1 H), 4.42 (t, J = 7.2 Hz, 2 H), 4.05 (m, 4 H), 3.35 (t, J = 17 ACS Paragon Plus Environment


6.6 Hz, 2 H), 1.99 (q, J = 7.2 Hz, 2 H), 1.79 (m, 2 H), 1.20-1.38 (m, 18 H).

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13

C NMR (150.8 MHz,

CDCl3)  136.5, 124.2 (d, J = 6.6 Hz), 68.2 (d, J = 5.4 Hz), 63.6 (d, J = 5.9 Hz), 34.0, 32.8, 32.1, 29.7, 29.3 (d, J = 3.3 Hz), 29.0, 28.8, 28.7, 28.1, 16.1 (d, J = 6.7 Hz). 14.1.IR (thin film): max 2925, 1266, 1035 cm-1. LRMS (EI): m/z (%) 398 (M+), 343, 43(100). HRMS (APCI-LTQ Orbitrap ) m/z: [M+H]+ Calculated for C16H33O4BrP: 399.1294; Found: 399.1292. Preparation of compound (E)-1f The (1b) (2.70 g, 8 mmol) was dissolved in THF (8 mL) at 0 °C and a solution of TBAF (1M in THF) (19.2 mL, 19.2 mmol) was added over a period of 5 min. The mixture was stirred for 2 h at room temperature and quenched by addition of saturated aqueous NH4Cl. The mixture was extracted three times with ether, the combined organic layers were dried over Na2SO4, and the solvent removed under reduced pressure. The residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 2:1) to provide (E)-1f (2.48 g, 89% yield) as a clear, pale yellow oil. 1H NMR (600 MHz, CDCl3) 5.73 (dt, J = 15.6 Hz, J = 6.6 Hz, 1 H), 5.53 (dt, J = 15.6 Hz, J = 6.6 Hz, 1 H), 4.42 (t, J = 7.2 Hz, 2 H), 4.05 (m, 4 H), 3.55 (t, J = 7.2 Hz, 2 H), 2.26 (s, 1 H), 1.99 (q, J = 6.6 Hz, 2 H), 1.50 (m, 2 H), 1.22-1.33 (m, 18 H). 13C NMR (150.8 MHz, CDCl3)  136.6, 124.2 (d, J = 6.5 Hz), 68.2 (d, J = 5.7 Hz), 63.6 (d, J = 5.9 Hz), 62.7, 32.7, 32.0, 29.4, 29.3, 29.2, 29.0, 28.7, 25.7, 16.0 (d, J = 6.6 Hz), 14.0. IR (thin film): max 3448, 2932, 1036 cm-1. LRMS (EI): m/z (%) 336(M+), 281, 207(100). HRMS (APCI-LTQ Orbitrap ) m/z: [M+H]+ Calculated for C16H34O5P: 337.2138; Found: 337.2138. Preparation of compounds (Z)-diethyl (3-phenylallyl) phosphate (Z)-1l. To a solution of Ethynylbenzene (1.07 mL, 10 mmol) in dried THF (10 mL), n-BuLi in n-hexane (12 mL, 1.5 M, 12 mmol) was added dropwise over 10 min at 0 °C under argon atmosphere. The reaction mixture was allowed to warm to RT and it was stirred for 1 h. Then the reaction mixture was cooled to 0 °C again and paraformaldehyde (369 mg, 12 mmol) was added. After that, the reaction mixture was allowed to warm to room temperature and stirred for another 12 h. The mixture was quenched by sat. 18 ACS Paragon Plus Environment

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NH4Cl aq. (15 mL), and was extracted with EA (3 × 20 mL). The combined organic phase was washed with brine (2 × 50 mL), dried over anhydrous Na2SO4. After filtered and concentrated under reduced pressure, the residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 10:1) to provide pure product 3-phenylprop-2-yn-1-ol (1.17 g, 89% yield). A mixture of 3-phenylprop-2-yn-1-ol (600 mg, 4.5 mmol), EA (8 mL), and Lindlar catalyst (40 mg) was stirred at room temperature under a hydrogen gas atmosphere for 1.5 h, After the reaction completed (monitored by 1H NMR), the mixture was filtered to give (Z)-3-phenylprop-2-en-1-ol (573 mg, 95% yield) as a pale yellow oil. The DMAP (61 mg, 0.5mmol) were placed in a 25 mL two-necked reaction flask at 0 oC temperature, which was filled with nitrogen by using the standard Schlenk technique. DCM (10 mL) was then added to the flask, (Z)-3-phenylprop-2-en-1-ol (268mg, 2 mmol) dissolved in DCM (5 ml) was added. Finally, Et3N (416 uL, 3 mmol) and diethyl phosphorochloridate (428 uL, 3 mmol) was added dropwise. The solution was stirred at 0 °C temperature for 4 h, and diluted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 7:3) to provide pure (Z)-1l (491mg, 91% yield) as a clear, pale yellow oil. This compound is known.22 1H NMR (600 MHz, CDCl3) 7.34 (t, J = 7.2 Hz, 2 H), 7.26 (t, J = 7.8 Hz, 1 H), 7.19 (d, J = 7.2 Hz, 2 H), 6.66 (d, J = 11.4Hz, 1 H), 5.81 (dt, J = 11.4 Hz, J = 6.6 Hz, 1 H), 4.80 (m, 2 H), 4.10 (m, 4 H), 1.31 (m, 6 H). Preparation of (Z)-diethyl tridec-2-en-1-yl phosphate (Z)-1p. To a solution of dodec-1-yne (998 mg, 6 mmol) in dried THF (10 mL), n-BuLi in n-hexane (3 mL, 2.4 M, 7.2 mmol) was added dropwise over 10 min at 0 °C under argon atmosphere. The reaction mixture was allowed to warm to RT and it was stirred for 1 h. Then the reaction mixture was cooled to 0 °C again and paraformaldehyde (216 mg, 7.2 mmol) was added. After that, the reaction mixture was allowed to warm to room temperature and stirred for another 12 h. The mixture was quenched by sat. NH4Cl aq. (15 mL), and was extracted with diethyl ether (3 × 20 mL). The combined organic phase was 19 ACS Paragon Plus Environment


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washed with brine (2 × 50 mL), dried over anhydrous Na2SO4. After filtered and concentrated under reduced pressure, the residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 10:1) to provide pure product tridec-2-yn-1-ol (0.94 g, 80% yield) as pale yellow oil. A mixture of tridec-2-yn-1-ol (196.3 mg, 2.5 mmol), EtOH (8 mL), pyridine (1.5 mL) and Lindlar catalyst (21 mg) was stirred at room temperature under a hydrogen gas atmosphere for 1 h. The mixture was filtered to give (Z)-tridec-2-en-1-ol (470 mg, 98 % yield) as pale yellow oil. The DMAP (61 mg, 0.5mmol) were placed in a 25 mL two-necked reaction flask at 0℃ temperature, which was filled with nitrogen by using the standard Schlenk technique. DCM (10 mL) was then added to the flask, (Z)-tridec-2-en-1-ol (397mg, 2 mmol) dissolved in DCM (5 mL) was added. Finally, Et3N (416 uL, 3 mmol) and diethyl phosphorochloridate (428 uL, 3 mmol) was added dropwise. The solution was stirred at 0 °C temperature for 4 h, and diluted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 7:3) to provide (Z)-1p (615 mg, 92% yield) as a clear, pale yellow oil. 1H NMR (600 MHz, CDCl3) 5.62 (dt, J = 10.8 Hz, J = 7.2 Hz, 1 H), 5.31 (dt, J = 10.8 Hz, J = 7.2 Hz, 1 H), 4.56 (t, J = 7.2 Hz, 2 H), 4.07 (m, 4 H), 2.04 (q, J = 7.2 Hz, 2 H), 1.38-1.22 (m, 22 H), 0.84 (t, J = 6.6 Hz, 3 H). 13C NMR (150.8 MHz, CDCl3)  135.3, 123.8 (d, J = 6.9 Hz), 63.6 (d, J = 5.9 Hz), 63.0 (d, J = 5.6 Hz), 31.8, 29.5, 29.4, 29.3, 29.2, 29.1, 27.4, 22.6, 16.0 (d, J = 6.6 Hz), 14.0. IR (thin film): max 2921, 1264, 1034 cm-1. LRMS (EI): m/z (%) 348(M+), 155, 67(100). HRMS (APCI-LTQ Orbitrap ) m/z: [M+H]+ Calculated for C18H38O4P: 349.2502; Found: 349.2501. Preparation of compound 7 and 8 To a stirring solution of 1.0 M in THF vinylmagnesium bromide (3.30 mL, 3.33 mmol) in THF (15 mL) at 0 °C was added aldehyde (3.0 mmol). After stirring for 1 hour, the reaction was quenched with 1 M HCl and the solvent was removed under reduced pressure. The resulting residue was then extracted with


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EA, and the organic layers were combined, washed with saturated NaHCO3, and dried over Na2SO4, and concentrated in vacuo to give the alcohol (B7 and B8) which was used in the next step. The DMAP (91.6 mg, 0.75 mmol) were placed in a 25 mL two-necked reaction flask at 0 °C temperature, which was filled with nitrogen by using the standard Schlenk technique. DCM (10 mL) was then added to the flask, alcohol (B7) (3.1 mmol) dissolved in DCM (5 mL) was added. Finally, Et3N (623.7 uL, 4.5 mmol) and diethyl phosphorochloridate (642.7 uL, 4.5 mmol) was added dropwise. The solution was stirred at 0 °C temperature for 4 h, and diluted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography (Petroleum ether / Ethyl ether =3:1) to provide 7 (882 mg, 82% yield) as a clear, pale yellow oil. 1H NMR (600 MHz, CDCl3)  5.80 (m, 1 H), 5.27 (d, J = 17.4 Hz, 1 H), 5.17 (d, J = 10.8 Hz, 1 H), 4.71 (m, 1 H), 4.06 (m, 4 H), 1.73-1.55 (m, 2 H), 1.33-1.22 (m, 24 H), 0.85 (t, J = 6.6 Hz, 3 H). 13C NMR (150.8 MHz, CDCl3) : 137.02 (d, J = 3.8 Hz), 117.0, 79.8 (d, J = 6.0 Hz), 63.5 (dd, J = 5.7 Hz, J = 4.2 Hz), 35.8 (d, J = 5.7 Hz), 31.9, 29.6, 29.5, 29.4, 29.3, 29.2, 29.1, 24.7, 22.6, 16.1 (dd, J = 6.9 Hz, J = 3.5 Hz), 14.1.IR (thin film): max 2922, 1265, 1033 cm-1. LRMS (EI): m/z (%) 348(M+), 207, 84(100). HRMS (APCI-TOF) m/z: [M+H]+ Calculated for C18H38O4P: 349.2502; Found: 349.2502. 1-Phenylprop-2-en-1-ol (B8) (0.5 mL, 3.79 mmol, 1.0 eq) was dissolved in dry THF (6 mL) and n-BuLi (1.5 M in hexanes, 2.5 mL, 3.75 mmol) was added dropwise at 0 °C. The reaction mixture was stirred for 30 min at 0 °C and diethyl chlorophosphate (0.55 mL, 3.8 mmol, 1.0 eq) was added dropwise at 0 °C. The reaction mixture was allowed to warm to rt and stirred for 2 h at rt. The reaction was quenched by addition of sat. aq. NH4Cl (10 mL) and then diluted with EtOAc (15 mL). The phases were separated and the aqueous phase was extracted with EtOAc (3  10 mL). The combined organic phases were washed with brine (10 mL), dried over MgSO4, filtered and concentrated in vacuo. The compound 8 (0.56 g, 92% pure, 1.91 mmol, 50%) was obtained as a pale yellow oil and used without further purification. 1H NMR (600 MHz, CDCl3): 7.37-7.30 (m, 5 H), 6.02 (m, 1 H), 5.78 (m, 1 H), 5.36 (d, J =



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17.4 Hz, 1 H), 5.24 (d, J = 10.2 Hz, 1 H), 4.07 (m, 2 H), 3.94 (m, 2 H), 1.26 (t, J = 7.2 Hz, 3 H), 1.17 (t, J = 7.2 Hz, 3 H). This compound is known.25 Preparation of bis(pentafluoroethyl)zinc reagent Zn(C2F5)2(DMPU)2. To an oven-dried 100-mL two-neck round-bottomed flask equipped with a magnetic stir bar were added Toluene (15 mL) and DMPU (2.4 mL, 20 mmol) under argon atmosphere. Pentafluoroethyl iodide (3.0 mL, 25 mmol) was added to the solution. Diethyl zinc solution (1.0 M in hexanes, 10 mL, 10 mmol) was then added dropwise at -35 °C. After the reaction mixture was stirred at -5 °C for 24 h, the precipitate was obtained. After removing the solution, the precipitate obtained was washed with hexane (50 mL) three times and dried under vacuum to give Zn(C2F5)2(DMPU)2 as a white powder (5.4 g, 95% yield). This compound is known.5b Preparation of bis(heptafluoropropyl)zinc reagent Zn(C3F7)2(DMPU)2 To an oven-dried 100-mL two-neck round-bottomed flask equipped with a magnetic stir bar were added Toluene (15 mL) and DMPU (2.4 mL, 20 mmol) under argon atmosphere. Heptafluoropropyl iodide (3.6 mL, 25 mmol) was added to the solution. Diethyl zinc solution (1.0 M in hexanes, 10 mL, 10 mmol) was then added dropwise at -35 °C. After the reaction mixture was stirred at -5 °C for 24 h, the precipitate was obtained. After removing the solution, the precipitate obtained was washed with hexane (50 mL) three times and dried under vacuum to give Zn(C3F7)2(DMPU)2 as a white powder (6.1 g, 93% yield). This compound is known.5b Preparation of bis(Perfluorobutyl)zinc reagent Zn(C4F9)2(DMPU)2. To an oven-dried 100-mL two-neck round-bottomed flask equipped with a magnetic stir bar were added Toluene (15 mL) and DMPU (2.4 mL, 20 mmol) under argon atmosphere. Perfluorobutyl iodide (4.3 mL, 25 mmol) was added to the solution. Diethyl zinc solution (1.0 M in hexanes, 10 mL, 10 mmol) was then added dropwise at -35 °C. After the reaction mixture was stirred at -5 °C for 24 h, the precipitate was obtained. After removing the solution, the precipitate obtained was washed with hexane (50 mL) three times and dried under vacuum to give Zn(C4F9)2(DMPU)2 as a white powder (6.9 g, 89% yield). This compound is known.5b 22 ACS Paragon Plus Environment

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Preparation of bis(tridecafluorohexyl)zinc reagent Zn(C6F13)2(DMPU)2 To an oven-dried 100-mL two-neck round-bottomed flask equipped with a magnetic stir bar were added Toluene (15 mL) and DMPU (2.4 mL, 20 mmol) under argon atmosphere. Tridecafluorohexyl iodide (5.4 mL, 25 mmol) was added to the solution. Diethyl zinc solution (1.0 M in hexanes, 10 mL, 10 mmol) was then added dropwise at -35 °C. After the reaction mixture was stirred at -5 °C for 24 h, the precipitate was obtained. After removing the solution, the precipitate obtained was washed with hexane (50 mL) three times and dried under vacuum to give Zn(C6F13)2(DMPU)2 as a white powder (8.4 g, 88% yield). This compound is known.5b General procedure for copper-catalyzed perfluoroalkylation of allyl phosphates. To a septum capped 25 mL of sealed tube were added Cu(acac)2 (10 mol%), L2 (10 mol%) and Zn(RF)2(DMPU)2 (1.0 equiv) under N2, followed by dioxane (2.0 mL) with stirring. Allyl phosphates (E)-1 (0.3 mmol) was then added subsequently. The sealed tube was screw capped and heated to 100 °C (oil bath). After stirring for 12 h, the reaction mixture was cooled to room temperature. The yield was determined by

19

F NMR before working up. If necessary, the reaction mixture was diluted with ethyl

acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified with silica gel chromatography to provide pure product. (E)-1,1,1,2,2,3,3,4,4-nonafluorooctadec-6-ene (3a). The product (From (E)-1a: 105.6 mg, 85% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  5.71 (dt, J = 15.6 Hz, 6.6 Hz, 1H), 5.38 (dt, J = 15.6 Hz, 7.2 Hz, 1 H) , 2.78 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.06 (q, J = 7.2 Hz, 2 H), 1.37-1.26 (m, 18 H), 0.88 (t, J = 7.2 Hz, 3 H). 13C NMR (150.8 MHz, CDCl3)  141.6, 124.9-120.6 (m, -(CF2)CF3), 118.2-115.4 (m, -(CF2)CF3)), 118.9 (t, J = 4.5 Hz, CH-CH2CF2), 117.6 (m), 115.9 (m), 37.2 (t, J = 22.3 Hz, CH-CH2CF2), 35.2, 34.6, 32.29, 32.27, 32.2, 32.1, 32.0, 31.7, 31.6, 25.3, 16.7. 19F NMR (564 MHz, CDCl3)  -81.2 (tt, J = 9.6 Hz, 2.3 Hz, 3F), -113.8 (m, 2F), -124.2 (m, 2F), -126.3 (m, 2F). IR (thin film): max 2924, 1224, 1133 cm-1.



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LRMS (EI): m/z (%) 414(M+), 343, 43(100). HRMS (ESI-TOF) m/z: Calculated for C18H27F9: 414.1969; Found: 414.1963. (E)-tert-butyldimethyl((13,13,14,14,15,15,16,16,16-nonafluorohexadec-10-en-1-yl)oxy)silane (3b). The product (From (E)-1b: 108.4 mg, 70% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  5.71 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 5.38 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 3.60 (t, J = 6.6 Hz, 2 H), 2.78 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.06 (q, J = 7.2 Hz, 2 H), 1.51 (m, 2 H), 1.39-1.28 (m, 12 H), 0.90 (s, 9 H), 0.05 (s, 6 H).

13

C NMR

(150.8 MHz, CDCl3)  141.8, 121.0-119.1 (m, -(CF2)CF3), 118.7 (t, J = 4.5 Hz, CH-CH2CF2), 118.0111.3 (m, -(CF2)CF3) 65.9, 37.4 (t, J = 22.5 Hz, CH-CH2CF2), 35.5, 35.2, 32.4, 32.2, 32.0, 32.0, 31.6, 31.5, 28.6, 28.4, -2.7. 19F NMR (564 MHz, CDCl3)  -81.2 (s, 3F), -113.8 (s, 2F), -124.2 (s, 2F) , -126.2 (s, 2F). IR (thin film): max 2933, 1237, 836 cm-1. LRMS (EI): m/z (%) 515(M+), 323, 267(100). HRMS (ESI-TOF) m/z: Calculated for C22H37F9OSi: 516.2470; Found: 516.2467. (E)-13,13,14,14,15,15,16,16-octafluorohexadec-10-en-1-yl acetate (3c). The product (From (E)-1c: 77.0 mg, 62% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 20:1). 1H NMR (600 MHz, CDCl3)  5.69 (dt, J = 15.0 Hz, 6.6 Hz, 1 H), 5.37 (dt, J = 15.0 Hz, 6.6 Hz, 1 H), 4.04 (t, J = 6.6 Hz, 2 H), 2.77 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.05 (m, 5 H), 1.60 (m, 2 H), 1.37-1.27 (m, 12 H).

13

C NMR (150.8 MHz, CDCl3)  173.8, 141.8, 121.5-119.1 (m, -(CF2)CF3),

118.8 (t, J = 4.2 Hz, CH-CH2CF2), 118.0-111.0 (m, -(CF2)CF3), 67.2, 37.4 (t, J = 22.4 Hz, CH-CH2CF2), 35.1, 32.0, 31.9, 31.8, 31.6, 31.5, 31.2, 28.5, 23.55. 19F NMR (564 MHz, CDCl3)  -81.3 (t, J = 9.6 Hz, 3F), -113.8 (m, 2F), -124.2 (m, 2F), -126.3 (m, 2F). IR (thin film): max 2934, 1748, 1232 cm-1. LRMS (EI): m/z (%) 384, 355, 43(100). HRMS (ESI-TOF) m/z: Calculated for C18H25F9O2: 444.1711; Found: 444.1712 (E)-diethyl (13,13,14,14,15,15,16,16,16-nonafluorohexadec-10-en-1-yl) phosphate (3d). The product (From (E)-1d: 97 mg, 60% yield) as a pale yellow oil was purified with silica gel chromatography 24 ACS Paragon Plus Environment

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(Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3)  5.66 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 5.34 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 4.07 (m, 4 H), 3.99 (q, J = 6.6 Hz, 2 H), 2.74 (td, J = 18.0 Hz, 6.6 Hz, 2 H), 2.02 (q, J = 7.2 Hz, 2 H), 1.63 (m, 2 H), 1.34-1.22 (m, 18 H). 13C NMR (150.8 MHz, CDCl3)  141.7, 121.2-119.0 (m, -(CF2)CF3), 118.7 (t, J = 4.4 Hz, CH-CH2CF2), 118.1-111.0 (m, -(CF2)CF3), 70.2 (d, J = 6.0 Hz), 66.2 (d, J = 6.0 Hz), 37.3 (t, J = 22.4 Hz, CH-CH2CF2), 35.1, 32.9, 32.8, 31.9, 31.6, 31.5, 31.4, 28.0, 18.7 (d, J = 6.8 Hz). 19F NMR (564 MHz, CDCl3)  -81.3 (t, J = 9.6 Hz, 3F), -113.8 (m, 2F), -124.2 (m, 2F), -126.3 (m, 2F). IR (thin film): max 2926, 1237 cm-1. LRMS (EI): m/z (%) 538(M+), 364, 155(100). HRMS (ESI-TOF) m/z: Calculated for C20H32F9O4P: 538.1894; Found: 538.1901. (E)-16-bromo-1,1,1,2,2,3,3,4,4-nonafluorohexadec-6-ene (3e). The product (From (E)-1e: 94.5 mg, 65% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1

H NMR (600 MHz, CDCl3)  5.70 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 5.38 (dt, J = 15.0 Hz, 7.2 Hz, 1 H),

3.40 (t, J = 6.6 Hz, 2 H), 2.78 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.06 (q, J = 6.6 Hz, 2 H), 1.85 (m, 2 H), 1.43-1.36 (m, 4 H), 1.29-1.26 (m, 8 H).

13

C NMR (150.8 MHz, CDCl3)  141.8, 123.3-119.1(m, -

(CF2)CF3), 118.8 (t, J = 4.2 Hz, CH-CH2CF2), 118.7-111.2 (m, -(CF2)CF3), 37.4 (t, J = 22.5 Hz, CHCH2CF2), 36.5, 35.5, 35.1, 32.0, 31.9, 31.6, 31.5, 31.3, 30.8. 19F NMR (564 MHz, CDCl3)  -81.2 (m, 3F), -113.7 (m, 2F), -124.2 (m, 2F), -126.2 (m, 2F). IR (thin film): max 2934, 1235 cm-1. LRMS (EI): m/z (%) 464(M+), 420, 69(100). HRMS (ESI-TOF) m/z: Calculated for C16H22F9Br: 464.0761; Found: 464.0757. (E)-13,13,14,14,15,15,16,16,16-nonafluorohexadec-10-en-1-ol (3f). The product (From (E)-1f: 76.0 mg, 63% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether =10:1). 1H NMR (600 MHz, CDCl3)  5.70 (dt, J = 15.0 Hz, 6.6 Hz, 1 H), 5.38 (dt, J = 15.0 Hz, 6.6 Hz, 1 H), 3.63 (t, J = 6.6 Hz, 2 H), 2.77 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.05 (q, J = 7.2 Hz, 2 H), 1.56 (m, 2 H), 1.38-1.28 (m, 13 H). 13C NMR (150.8 MHz, CDCl3)  141.8, 121.7-119.1 (m, -(CF2)CF3), 118.7 (t, J = 22.4 Hz, CH-CH2CF2), 118.0-111.2 (m, -(CF2)CF3), 65.7, 37.4 (t, J = 22.6 Hz, CHCH2CF2), 35.4, 35.2, 32.1, 32.0, 32.0, 31.6, 31.5, 28.4. 19F NMR (564 MHz, CDCl3)  -81.2 (t, J = 11.3 25 ACS Paragon Plus Environment


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Hz, 3F), -113.7 (m, 2F), -124.2 (m, 2F), -126.2 (m, 2F). IR (thin film): max 3388, 2933, 1237 cm-1. LRMS (EI): m/z (%) 402(M+), 401, 55(100). HRMS (ESI-TOF) m/z: Calculated for C16H23F9O: 402.1605; Found: 402.1594. (E)-8,8,9,9,10,10,11,11,11-nonafluoro-4-methylundec-5-ene (3g). The product (From (E)-1g: 60.4 mg, 61% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)).1H NMR (600 MHz, CDCl3)  5.57 (dd, J = 15.6 Hz, 7.8 Hz, 1 H), 5.34 (dt, J = 15.6 Hz, 6.6 Hz, 1 H), 2.78 (td, J = 18.0 Hz, 6.6Hz, 2 H), 2.17 (m, 1 H), 1.26 (m, 4 H), 0.98 (d, J = 6.6 Hz, 3 H), 0.88 (t, J = 6.6 Hz, 3 H). 13C NMR (150.8 MHz, CDCl3)  147.6, 121.5-118.9 (m, -(CF2)CF3), 117.0 (t, J = 4.4 Hz, CH-CH2CF2), 116.9-110.0 (m, -(CF2)CF3), 41.5, 39.3, 37.4 (t, J = 22.3 Hz, CH-CH2CF2), 32.3, 22.9 (d, J = 2.0 Hz), 16.7. 19F NMR (564 MHz, CDCl3)  -81.2 (m, 3F), -113.7 (m, 2F), -124.2 (m, 2F), -126.2 (m, 2F). IR (thin film): max 2952, 1311, 514 cm-1. LRMS (EI): m/z (%) 330(M+), 287, 69(100). HRMS (ESI-TOF) m/z: Calculated for C12H15F9: 330.1030; Found: 330.1028. (E)-(4,4,5,5,6,6,7,7,7-nonafluorohept-1-en-1-yl)cyclohexane (3h). The product (From (E)-1h: 65.6 mg, 64% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)).1H NMR (600 MHz, CDCl3)  5.66 (dd, J = 16.0 Hz, 7.2 Hz, 1 H), 5.35 (dt, J = 16.0 Hz, 7.2 Hz, 1 H), 2.77 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.00 (m, 1 H), 1.72 (d, J = 10.2 Hz, 2 H), 1.30-1.85 (m, 8 H).

13

C NMR (150.8 MHz, CDCl3)  147.4, 121.0-117.2 (m, -(CF2)CF3), 116.4 (t, J = 4.4 Hz, CH-

CH2CF2), 115.2-110.0 (m, -(CF2)CF3), 43.4, 37.5 (t, J = 22.5 Hz, CH-CH2CF2), 35.2, 32.4, 28.7, 28.5. 19

F NMR (564 MHz, CDCl3)  -81.3 (m, 3F), -113.8 (m, 2F), -124.1 (m, 2F), -126.2 (m, 2F). IR (thin

film): max 2917, 1232 cm-1. LRMS (EI): m/z (%) 342(M+), 313, 81(100). HRMS (ESI-TOF) m/z: Calculated for C13H15F9: 342.1030; Found: 342.1032. (E)-(5,5,6,6,7,7,8,8,8-nonafluorooct-2-en-1-yl)benzene (3i). The product (From (E)-1i: 53.5 mg, 51% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  7.37 (t, J = 7.2 Hz, 2 H), 7.28 (t, J = 7.8 Hz, 1 H), 7.25 (d, J = 7.2 Hz, 2 H), 26 ACS Paragon Plus Environment

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 5.94 (dt, J = 15.0 Hz, 6.6 Hz, 1 H), 5.57 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 3.48 (d, J = 7.2 Hz, 2 H), 2.89 (td, J = 29.4 Hz, 7.2 Hz, 2 H).

13

C NMR (150.8 MHz, CDCl3)  142.1, 140.1, 131.2, 131.2, 130.0,

123.2-120.9 (m, -(CF2)CF3), 120.5 (t, J = 4.2 Hz, CH-CH2CF2), 120.0-117.1 (m, -(CF2)CF3), 41.6, 37.3 (t, J = 22.5 Hz, CH-CH2CF2). 19F NMR (564 MHz, CDCl3)  -81.2 (m, 3F), -113.5 (m, 2F), -124.1 (m, 2F) , -126.2 (m, 2F). IR (thin film): max 3030, 1243, 1130 cm-1. LRMS (EI): m/z (%) 350(M+), 331, 117(100). HRMS (ESI-TOF) m/z: Calculated for C14H11F9: 350.0717; Found: 350.0711. (E)-(6,6,7,7,8,8,9,9,9-nonafluoronon-3-en-1-yl)benzene (3j). The product (From (E)-1j: 60.1 mg, 55% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  7.31 (t, J = 7.2 Hz, 2 H), 7.21 (m, 3 H), 5.80 (dt, J = 15.6 Hz, 6.6 Hz, 1 H), 5.45 (dt, J = 15.6 Hz, 6.6 Hz, 1 H), 2.80 (td, J = 18.0 Hz, 7.2 Hz, 2 H), 2.73 (t, J = 7.2 Hz, 2 H), 2.42 (q, J = 7.2 Hz, 2 H). 13C NMR (150.8 MHz, CDCl3)  144.0, 140.7, 131.1, 131.0, 128.8, 123.1-119.8 (m, (CF2)CF3), 119.7 (t, J = 4.2 Hz, CH-CH2CF2), 119.3-111.0 (m, -(CF2)CF3), 38.0, 37.4 (t, J = 22.5 Hz, CH-CH2CF2), 37.0. 19F NMR (564 MHz, CDCl3)  -81.1 (m, 3F), -113.6 (m, 2F), -124.1 (m, 2F), -126.1 (m, 2F). IR (thin film): max 2929, 1236 cm-1. LRMS (EI): m/z (%) 364(M+), 287, 91(100). HRMS (ESITOF) m/z: Calculated for C15H13F9: 364.0874; Found: 364.0872. (E)-1,1,1,2,2,3,3,4,4-nonafluoro-7-methylhexadec-6-ene (3k). The product (From (E)-1k: 42.0 mg, 35% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1

H NMR (600 MHz, CDCl3)  5.17 (t, J = 7.2 Hz, 1 H), 2.81 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.05 (t, J =

7.2 Hz, 2 H), 1.64 (s, 3 H), 1.40 (m, 2 H), 1.31-1.26 (m, 12 H), 0.88 (t, J = 6.6 Hz, 3 H).

13

C NMR

(150.8 MHz, CDCl3)  141.3, 118.2-108.3 (m, -(CF2)CF3), 108.0 (t, J = 4.2 Hz, CH-CH2CF2), 107.8106.5 (m, -(CF2)CF3), 37.6, 29.8, 28.0 (t, J = 22.3 Hz, CH-CH2CF2), 27.6, 27.4, 27.2, 27.0, 25.5, 20.6, 14.1, 11.9. 19F NMR (564 MHz, CDCl3)  -84.9 (m, 3F), -117.2 (m, 2F), -127.9 (m, 2F), -129.9 (m, 2F). IR (thin film): max 2938, 1745, 1233 cm-1. LRMS (EI): m/z (%) 400(M+), 288, 69(100). HRMS (ESITOF) m/z: Calculated for C17H25F9: 400.1813; Found: 400.1806. 27 ACS Paragon Plus Environment


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(E)-(4,4,5,5,6,6,7,7,7-nonafluorohept-1-en-1-yl)benzene (3l). The product (From (E)-1l: 40 mg, 40% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  7.40 (d, J = 7.2 Hz, 2 H), 7.35 (t, J = 7.2 Hz, 2 H), 7.28 (t, J = 7.2 Hz, 1 H), 6.63 (d, J = 16.2 Hz, 1 H), 6.15 (dt, J = 16.2 Hz, 7.2 Hz, 1 H), 3.01 (td, J = 18.0 Hz, 7.2 Hz, 2 H). 19F NMR (564 MHz, CDCl3)  -80.0 (m, 3F), -113.1 (m, 2F), -124.0 (m, 2F), -126.1 (m, 2F). This compound is known.26 (E)-1-methyl-4-(4,4,5,5,6,6,7,7,7-nonafluorohept-1-en-1-yl)benzene (3m). The product (From (E)-1m: 43mg, 41% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%). 1H NMR (600 MHz, CDCl3)  7.30 (d, J = 7.8 Hz, 2 H), 7.16 (d, J = 7.8 Hz, 2 H), 6.60 (d, J = 15.6 Hz, 1 H), 6.10 (dt, J = 15.6 Hz, 7.2 Hz, 1 H), 3.01 (td, J = 18.0 Hz, 7.2 Hz, 2 H), 2.36 (s, 3 H). 13C NMR (150.8 MHz, CDCl3)  140.7, 139.8, 136.1, 132.0, 129.0, 123.2 (m, -(CF2)CF3), 117.5 (t, J = 4.5 Hz, CH-CH2CF2), 115.3-109.3 (m, -(CF2)CF3), 37.8 (t, J = 22.6 Hz, CH-CH2CF2), 23.8. 19F NMR (564 MHz, CDCl3)  -81.1 (m, 3F), -113.2 (m, 2F), -124.0 (m, 2F), -126.1 (m, 2F). IR (thin film): max 2924, 1239 cm-1. LRMS (EI): m/z (%) 350(M+), 311, 131(100). HRMS (ESI-TOF) m/z: Calculated for C14H11F9: 350.0717; Found: 350.0705. (E)-1-(tert-butyl)-4-(4,4,5,5,6,6,7,7,7-nonafluorohept-1-en-1-yl)benzene (3n). The product (From (E)-1n: 53 mg, 45% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  7.37 (d, J = 8.4 Hz, 2 H), 7.34 (d, J = 8.4 Hz, 2 H), 6.61 (d, J = 16.0 Hz, 1 H), 6.10 (dt, J = 16.0 Hz, 7.2 Hz, 1 H), 3.01 (td, J = 18.0 Hz, J = 7.2 Hz 2 H), 1.33 (s, 9 H). 13C NMR (150.8 MHz, CDCl3)  154.0, 139.7, 136.1, 128.8, 128.2, 121.6-117.7 (m, -(CF2)CF3), 117.8 (t, J = 4.4 Hz, CH-CH2CF2), 113.5-111.2 (m, -(CF2)CF3), 37.8 (t, J = 22.8 Hz, CH-CH2CF2), 37.3, 33.8.

19

F NMR (564 MHz, CDCl3)  -76.7 (s, 3F), -108.8 (m, 2F), -119.7 (s, 2F), -121.7 (m, 2F). IR

(thin film): max 2958, 1230, 1132 cm-1. LRMS (EI): m/z (%) 392(M+), 377(100), 349. HRMS (ESI-TOF) m/z: Calculated for C17H17F9: 392.1187; Found: 392.1183.


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(E)-1-methoxy-3-(4,4,5,5,6,6,7,7,7-nonafluorohept-1-en-1-yl)benzene (3o). The product (From (E)1o: 41.7 mg, 38% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether =20:1). 1H NMR (600 MHz, CDCl3)  7.26 (t, J = 7.8 Hz, 1 H), 6.99 (d, J = 7.8 Hz, 1 H), 6.93 (s, 1 H), 6.84 (dd, J = 8.4 Hz, 2.4 Hz, 1 H), 6.6 (d, J = 15.6 Hz, 1 H), 6.14 (dt, J = 15.6 Hz, 7.2 Hz, 1 H), 3.83 (s, 3 H), 3.01 (td, J = 18.0 Hz, 7.2 Hz, 2 H).

13

C NMR (150.8 MHz, CDCl3)  162.5,

140.3, 139.8, 132.3, 128.8, 121.7, 121.5-119.3 (m, -(CF2)CF3), 118.9 (t, J = 4.4 Hz, CH-CH2CF2), 118.3-109.2 (m, -(CF2)CF3), 116.4, 114.5, 57.8, 37.7 (t, J = 22.8 Hz, CH-CH2CF2). 19F NMR (564 MHz, CDCl3)  -81.1 (t, J = 9.6 Hz, 3F), -113.2 (m, 2F), -124.6 (m, 2F), -126.1 (m, 2F). IR (thin film): max 2988, 1230 cm-1. LRMS (EI): m/z (%) 366(M+), 347, 147(100). HRMS (ESI-TOF) m/z: Calculated for C14H11OF9: 366.0666; Found: 366.0660. (E)-1,1,1,2,2-pentafluorohexadec-4-ene (4a). The product (From (E)-1a: 69.7 mg, 74% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  5.70 (dt, J = 15.6 Hz, 6.6 Hz, 1 H), 5.37 (dt, J = 15.6 Hz, 6.6 Hz, 1 H), 2.74 (td, J = 17.4 Hz, 6.6 Hz, 2 H), 2.06 (m, 2 H), 1.37-1.26 (m, 18 H), 0.88 (m, 3 H). 13C NMR (150.8 MHz, CDCl3)  141.6, 124.9-119.2 (m, -(CF2)CF3), 118.9 (t, J = 4.5 Hz, CH-CH2CF2), 118.7-111.1 (m, -(CF2)CF3), 37.3 (t, J = 22.3 Hz, CH-CH2CF2), 35.1, 34.6, 32.3, 32.3, 32.2, 32.1, 32.0, 31.7, 31.5, 25.3, 16.7.

19

F

NMR (564 MHz, CDCl3)  -84.8 (m, 3F), -117.4 (t, J = 17.0 Hz, 2F). IR (thin film): max 2917, 1198 cm-1. LRMS (EI): m/z (%) 315 (M++H+), 314(M+), 70(100). HRMS (ESI-TOF) m/z: Calculated for C16H27F5: 314.2033; Found: 314.2024. (E)-1,1,1,2,2,3,3-heptafluoroheptadec-5-ene (5a). The product (From (E)-1a: 76.4 mg, 70% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  5.71 (dt, J = 18.2 Hz, 6.6 Hz, 1 H), 5.39 (dt, J = 15.0 Hz, 6.6 Hz, 1 H), 2.77 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.07 (q, J = 7.2 Hz, 2 H), 1.39-1.26 (m, 18 H), 0.88 (t, J = 6.6 Hz, 3 H). 13C NMR (150.8 MHz, CDCl3)  141.6, 123.6-119.1 (m, -(CF2)CF3), 118.7 (t, J = 4.2 Hz, CH-CH2CF2), 117.9109.5 (m, -(CF2)CF3), 37.2 (t, J = 22.6 Hz, CH-CH2CF2), 35.2, 34.6, 32.3, 32.3, 32.2, 32.1, 32.0, 31.7, 29 ACS Paragon Plus Environment


31.5, 25.3, 16.7.

19

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F NMR (564 MHz, CDCl3)  -80.8 (s, 3F), -114.5 (s, 2F), -127.6 (s, 2F). IR (thin

film): max 2931, 1227 cm-1. LRMS (EI): m/z (%) 364 (M+), 308, 48(100). HRMS (ESI-TOF) m/z: Calculated for C17H27F7: 364.2001; Found: 364.2014. (E)-1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoroicos-8-ene (6a). The product (From (E)- 1a: 94.1 mg, 61% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  5.71 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 5.39 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 2.78 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.07 (q, J = 7.2 Hz, 2 H), 1.39-1.27 (m, 18 H), 0.88 (t, J = 7.2 Hz, 3 H). 13

C NMR (150.8 MHz, CDCl3)  141.8, 123.2-119.2 (m, -(CF2)CF3), 118.7 (t, J = 4.2 Hz, CH-CH2CF2),

118.0-109.2 (m, -(CF2)CF3), 37.6 (t, J = 22.5 Hz, CH-CH2CF2), 35.2, 34.6, 32.3, 32.3, 32.2, 32.1, 32.0, 31.7, 31.5, 25.3, 16.7. 19F NMR (564 MHz, CDCl3)  -80.1 (t, J = 10.8 Hz 3F), -113.5 (m, 2F), -122.1 (s, 2F), -123.0 (s, 2F), -123.2 (s, 2F), -127.6 (m, 2F). IR (thin film): max 2930, 1239, cm-1. LRMS (EI): m/z (%) 514 (M+), 486, 43(100). HRMS (ESI-TOF) m/z: Calculated for C20H27F13: 514.1905; Found: 514.1910. (E)-tert-butyl((15,15,16,16,17,17,17-heptafluoroheptadec-12-en-1-yl)oxy)dimethylsilane (5b). The product (From (E)-1b: 93.7 mg, 67% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  5.70 (dt, J = 15.6 Hz, 6.6 Hz, 1 H), 5.38 (dt, J = 15.0 Hz, 6.6 Hz, 1 H), 3.60 (t, J = 6.6 Hz, 2 H), 2.76 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.06 (q, J = 6.6 Hz, 2 H), 1.51-1.26 (m, 14 H), 0.90 (s, 9 H), 0.05 (s, 6 H).

13

C NMR (150.8 MHz,

CDCl3)  141.8, 12123.6-119.1 (m, -(CF2)CF3), 118.7 (t, J = 4.2 Hz, CH-CH2CF2), 118.0-109.5 (m, (CF2)CF3), 65.9, 37.2 (t, J = 22.5 Hz, CH-CH2CF2), 35.5, 35.2, 32.3, 32.2, 32.0, 32.0, 31.6, 31.5, 28.6, 28.4, -2.7. 19F NMR (564 MHz, CDCl3)  -80.7 (t, J = 10.8 Hz, 3F), -114.4 (m, 2F), -127.5 (m, 2F). IR (thin film): max 2931, 1227 cm-1. LRMS (EI): m/z (%) 465, 409, 69(100). HRMS (ESI-TOF) m/z: Calculated for C21H37F7OSi: 466.2502; Found: 466.2503.


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(E)-tert-butyldimethyl((15,15,16,16,17,17,18,18,19,19,20,20,20-tridecafluoroicos-12-en-1-yl)oxy) silane (6b). The product (From (E)-3b: 96.1 mg, 52% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  5.71 (dt, J = 16.0 Hz, 6.6 Hz, 1 H), 5.38 (dt, J = 15.0 Hz, 6.6 Hz, 1 H), 3.60 (t, J = 6.6 Hz, 2 H), 2.77 (td, J = 18.6 Hz, 6.6 Hz, 2 H), 2.06 (q, J = 7.2 Hz, 2 H), 1.52-1.26 (m, 14 H), 0.89 (s, 9 H), 0.05 (s, 6 H). 13C NMR (150.8 MHz, CDCl3)  139.1, 121.6-116.2 (m, -(CF2)CF3), 116.1 (t, J = 4.2 Hz, CH-CH2CF2), 116.0-108.1 (m, -(CF2)CF3), 63.2, 37.4 (t, J = 22.8 Hz, CH-CH2CF2), 32.8, 32.5, 29.5, 29.4, 29.3, 29.0, 28.8, 25.9, 25.7, 18.3, -5.4. 19F NMR (564 MHz, CDCl3)  -80.9 (m, 3F), -113.5 (s, 2F), -122.1 (s, 2F) , -123.0 (s, 2F), 123.2 (m, 2F), -126.2 (m, 2F). IR (thin film): max 2934, 1240 cm-1. LRMS (EI): m/z (%) 615(M+), 559, 83(100). HRMS (ESI-TOF) m/z: [M]+ Calculated for C24H37F13OSi: 616.2406; Found: 616.2415. (E)-diethyl(13,13,14,14,15,15,15-heptafluoropentadec-10-en-1-yl)phosphate

(5d).

The

product

(From (E)-1d: 93.7 mg, 64% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3)  5.68 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 5.36 (dt, J = 16.0 Hz, 7.2 Hz, 1 H), 4.09 (m, 4 H), 4.00 (q, J = 6.6 Hz, 2 H), 2.75 (td, J = 18.6 Hz, 6.6 Hz, 2 H), 2.03 (q, J = 7.2 Hz, 2 H), 1.65 (m, 2 H), 1.35-1.23 (m, 18 H). 13C NMR (150.8 MHz, CDCl3)  141.7, 123.5-119.0 (m, -(CF2)CF3), 118.7 (t, J = 4.2 Hz, CH-CH2CF2), 118.0-109.5 (m, -(CF2)CF3), 70.3 (d, J = 6.0 Hz), 66.2 (d, J = 5.7 Hz), 37.1 (t, J = 22.6 Hz, CH-CH2CF2), 35.1, 32.8, 32.0, 31.9, 31.7, 31.5, 31.5, 28.0, 18.7. 19F NMR (564 MHz, CDCl3)  -80.7 (m, 3F), -114.5 (m, 2F), -127.6 (s, 2F). IR (thin film): max 2934, 1228, 1038 cm-1. IR (thin film): max 2934, 1228, 1038 cm-1. LRMS (EI): m/z (%) 488(M+), 364, 155(100). HRMS (ESI-TOF) m/z: Calculated for C19H32F7O4P: 488.1926; Found: 488.1915. (E)-diethyl(13,13,14,14,15,15,16,16,17,17,18,18,18-tridecafluorooctadec-10-en-1-yl) phosphate (6d). The product (From (E)-1d: 93.8 mg, 49% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether / Ethyl ether = 3:1). 1H NMR (600 MHz, CDCl3)  5.68 (dt, J = 16.0 Hz, 6.6 Hz, 1 H), 5.36 (dt, J = 16.0 Hz, 6.6 Hz, 1 H), 4.09 (m, 4 H), 4.00 (q, J = 6.6 Hz, 2 H), 2.74 (td, J 31 ACS Paragon Plus Environment


Page 32 of 39

= 18.0 Hz, 7.2 Hz, 2 H), 2.04 (q, J = 6.6 Hz, 2 H), 1.65 (m, 2 H), 1.36-1.23 (m, 18 H). 13C NMR (150.8 MHz, CDCl3)  141.8, 123.5-118.9 (m, -(CF2)CF3), 118.9 (t, J = 4.2 Hz, CH-CH2CF2), 118.0-110.0 (m, -(CF2)CF3), 70.3 (d, J = 6.0 Hz), 66.2 (d, J = 5.9 Hz), 37.4 (t, J = 22.6 Hz, CH-CH2CF2), 35.1, 32.9, 32.8, 32.0, 31.9, 31.7, 31.6, 31.5, 28.0, 18.7. 19F NMR (564 MHz, CDCl3)  -80.9 (m, 3F), -113.5 (m, 2F), -112.1 (s, 2F) -123.0 (s, 2F), -123.0 (m, 2F), -126.3 (m, 2F). IR (thin film): max 2941, 1245, 1030 cm-1. LRMS (EI): m/z (%) 639(M++H+), 638(M+), 155(100). HRMS (ESI-TOF) m/z: Calculated for C22H32F13O4P : 638.1831; Found: 638.1833. (E)-8,8,9,9,10,10,11,11,11-nonafluoro-4-methylundec-5-ene (4g). The product (From (E)-1g: 40.7 mg, 59% yield) as a colorless oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  5.57 (dd, J = 16.0 Hz, 8.4 Hz, 1 H), 5.35 (dt, J = 16.0 Hz, 7.2 Hz, 1 H), 2.77 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.18 (m, 1 H), 1.31 (m, 4 H), 0.99 (d, J = 6.6 Hz, 3 H), 0.89 (t, J = 7.2 Hz, 3 H).

13

C NMR (150.8 MHz, CDCl3)  147.6, 122.7-117.2 (m, -CF2CF3), 117.0 (t, J = 4.4 Hz, CH-

CH2CF2), 116.7-109.5 (m, -CF2CF3), 41.5, 39.3, 37.4 (t, J = 22.5 Hz, CH-CH2CF2), 22.9, 22.9, 16.7. 19F NMR (564 MHz, CDCl3)  -87.3 (s, 3F), -119.8 (t, J = 17.5 Hz, 2F). IR (thin film): max 2930, 1100, 463 cm-1. LRMS (EI): m/z (%) 230(M+), 215, 69(100). HRMS (ESI-TOF) m/z: Calculated for C10H15F5: 230.1094; Found: 230.1095. (E)-1,1,1,2,2,3,3-heptafluoro-7-methyldec-5-ene (5g). The product (From (E)-1g: 50.4 mg, 60% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)).1H NMR (600 MHz, CDCl3)  5.57 (dd, J = 15.0 Hz, 8.4 Hz, 1 H), 5.35 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 2.77 (td, J = 18.6 Hz, 7.2 Hz, 2 H), 2.18 (m, 1 H), 1.27 (m, 4 H), 0.99 (d, J = 6.6 Hz, 3 H), 0.89 (t, J = 7.2 Hz, 3 H). 13

C NMR (150.8 MHz, CDCl3)  147.6, 121.7-117.4 (m, -(CF2)CF3), 117.0 (t, J = 4.4 Hz, CH-CH2CF2),

114.0-109.8 (m, -(CF2)CF3), 41.5, 39.3, 37.2 (t, J = 22.6 Hz, CH-CH2CF2), 22.9, 22.9, 16.6. 19F NMR (564 MHz, CDCl3)  -83.4 (t, J = 9.6 Hz, 3F), -117.0 (s, 2F), -130.1 (m, 2F). IR (thin film): max 2920, 1100, 474 cm-1. LRMS (EI): m/z (%) 280(M+), 187, 69(100). HRMS (ESI-TOF) m/z: Calculated for C11H15F7: 280.1062; Found: 280.1069. 32 ACS Paragon Plus Environment

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(E)-(4,4,5,5,5-pentafluoropent-1-en-1-yl)benzene (4l). The product (From (E)-1l: 31.8 mg, 45% yield) as a colorless oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  7.39 (d, J = 7.8 Hz, 2 H), 7.34 (t, J = 7.8 Hz, 2 H), 7.28 (t, J = 7.2 Hz, 1 H), 6.62 (d, J = 16.2 Hz, 1 H), 6.13 (dt, J = 16.2 Hz, 8.0 Hz, 1 H), 2.97 (td, J = 17.4 Hz, J = 7.2 Hz, 2 H). 19F NMR (564 MHz, CDCl3)  -87.4 (m, 3F), -119.5 (m, 2F). This compound is known.27 (E)-(4,4,5,5,6,6,6-heptafluorohex-1-en-1-yl)benzene (5l). The product (From (E)-1l: 236 mg, 42% yield) as a colorless oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  7.39 (d, J = 7.2 Hz, 2 H), 7.34 (t, J = 7.2 Hz, 2 H), 7.28 (t, J = 7.2 Hz, 1 H), 6.63 (d, J = 16.0 Hz, 1 H), 6.14 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 3.02 (td, J = 18.0 Hz, J = 7.2 Hz, 2 H). 19F NMR (564 MHz, CDCl3)  -80.6 (t, J = 9.6 Hz, 3F), -113.9 (m, 2F) , -127.4 (d, J = 3.4 Hz, 2F). This compound is known.27 (E)-1-(tert-butyl)-4-(4,4,5,5,5-pentafluoropent-1-en-1-yl)benzene (4n). The product (From (E)-1n: 41.2 mg, 47% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  7.38 (d, J = 8.4 Hz, 2 H), 7.35 (d, J = 8.4 Hz, 2 H), 6.62 (d, J = 16.0 Hz, 1 H), 6.12 (dt, J = 16.0 Hz, 7.2 Hz, 1 H), 2.97 (td, J = 17.4 Hz, J = 7.2 Hz, 2 H), 1.35 (s, 9 H). 13

C NMR (150.8 MHz, CDCl3)  154.0, 139.5, 136.1, 128.9, 128.3, 131.1-115.9 (m, -CF2CF3), 117.9 (t,

J = 4.4 Hz, CH-CH2CF2), 37.6 (t, J = 22.5 Hz, CH-CH2CF2), 37.3, 33.9. 19F NMR (564 MHz, CDCl3)  -80.5 (s, 3F), -112.7 (t, J = 17.5 Hz, 2F). IR (thin film): max 2960, 1190 cm-1. LRMS (EI): m/z (%) 292(M+), 277(100), 249. HRMS (ESI-TOF) m/z: Calculated for C15H17F5: 292.1250; Found: 292.1257. (E)-1-(tert-butyl)-4-(4,4,5,5,6,6,6-heptafluorohex-1-en-1-yl)benzene (5n). The product (From (E)-1n: 45.2 mg, 44% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  7.38 (d, J = 8.4 Hz, 2 H), 7.34 (d, J = 8.4 Hz, 2 H), 6.61 (d, J = 16.0 Hz, 1 H), 6.10 (dt, J = 16.0 Hz, 7.2 Hz, 1 H), 3.00 (td, J = 16.8 Hz, J = 7.2 Hz, 2 H), 1.32 (s, 9 H). 13

C NMR (150.8 MHz, CDCl3)  154.0, 139.6, 136.1, 128.8, 128.2, 128.8-117.7 (m, -(CF2)CF3), 117.8 33 ACS Paragon Plus Environment


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(t, J = 4.4 Hz, CH-CH2CF2), 37.6 (t, J = 22.6 Hz, CH-CH2CF2), 37.3, 33.9. 19F NMR (564 MHz, CDCl3)  -80.6 (m, 3F), -113.9 (m, 2F), -127.4 (m, 2F). IR (thin film): max 2960, 1220, 1110 cm-1. LRMS (EI): m/z (%) 342(M+), 327(100), 290. HRMS (ESI-TOF) m/z: Calculated for C16H17F7: 342.1218; Found: 342.1213. (E)-1,1,1,2,2,3,3,4,4-nonafluoroheptadec-6-ene (3p). The product (From (E)-1p: 105.7 mg, 88% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1H NMR (600 MHz, CDCl3)  5.71 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 5.37 (dt, J = 15.6 Hz, 7.2 Hz, 1 H), 2.78 (td, J = 6.6 Hz, 7.2 Hz, 2 H), 2.06 (m, 2 H), 1.39-1.27 (m, 16 H), 0.89 (t, J = 6.6 Hz, 3 H). 13C NMR (150.8 MHz, CDCl3)  141.8, 123.2 (m, -(CF2)CF3), 118.7 (t, J = 4.2 Hz, CH-CH2CF2), 117.2-109.4 (m, (CF2)CF3), 37.4 (t, J = 22.5 Hz, CH-CH2CF2), 35.2, 34.6, 32.4, 32.2, 32.1, 32.0, 31.7, 31.5, 25.3, 16.7. 19

F NMR (564 MHz, CDCl3)  -81.2 (td, J = 9.6 Hz, 2.3 Hz, 3 H), -113.8 (m, 2F), -124.2 (m, 2F), -

126.2 (m, 2F). IR (thin film): max 2938, 1239 cm-1. LRMS (EI): m/z (%) 400(M+), 372, 48(100). HRMS (ESI-TOF) m/z: Calculated for C17H25F9: 400.1813; Found: 400.1811. (E)-1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorononadec-8-ene (6p). The product (From (E)-1p: 106.5 mg, 71% yield) as a pale yellow oil was purified with silica gel chromatography (Petroleum ether (100%)). 1

H NMR (600 MHz, CDCl3)  5.70 (dt, J = 15.0 Hz, 7.2 Hz, 1 H), 5.37 (dt, J = 16.0 Hz, 7.2 Hz, 1 H),

2.78 (td, J = 19.0 Hz, 7.2 Hz, 2 H), 2.06 (m, 2 H), 1.39-1.27 (m, 16 H), 0.88 (t, J = 6.6 Hz, 3 H). 13C NMR (150.8 MHz, CDCl3)  141.8, 123.2 (m, -(CF2)CF3), 118.7 (t, J = 4.2 Hz, CH-CH2CF2), 117.0109.0 (m, -(CF2)CF3), 37.4 (t, J = 22.6 Hz, CH-CH2CF2), 35.2, 34.5, 32.3, 32.2, 32.1, 32.0, 31.7, 31.5, 25.3, 16.6. 19F NMR (564 MHz, CDCl3)  -81.0 (m, 3 H), -113.5 (m, 2F), -122.1 (m, 2F), -123.0 (s, 2F), -123.2 (s, 2F), -126.3 (s, 2F). IR (thin film): max 2927, 1656, 1238 cm-1. LRMS (EI): m/z (%) 500(M+), 472，43(100). HRMS (ESI-TOF) m/z: Calculated for C19H25F13: 500.1749; Found: 500.1741.

ASSOCIATED CONTENT 34 ACS Paragon Plus Environment

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Supportiong Information. The Supporting Information is available free of charge on the ACS Publications website. Preparation of allyl phosphates, copies of 1H, 19F and 13C NMR spectra for compounds.

ACKNOWLEDGMENTS. This work was financially supported by the National Natural Science Foundation of China (grant number: 21602041), the Natural Science Foundation of Anhui Province (grant number: 1708085QB38), Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering (grant number: 45000-411104/007), and Start-up Foundation of Hefei University of Technology. We thank Prof. Chun-Yang He and Dr. Ji-Wei Gu for helpful discussions.

REFERENCES. (1) For selected reviews, see: (a) Tsuji, J.; John Wiley & Sons: Chichester, UK, 2004; (b) Trost, B. M.; Toste, F. D. Enantioselective Total Synthesis of (−)-Galanthamine. J. Am. Chem. Soc. 2000, 122, 11262; (c) Trost, B. M.; Thiel, O. R.; Tsui, H.-C. DYKAT of Baylis−Hillman Adducts: Concise Total Synthesis of Furaquinocin E. J. Am. Chem. Soc. 2002, 124, 11616; (d) Heumann, A.; Wiley-VCH: Weinheim, Germany, 2004; Vol. 1; (e) Demotie, A.; Fairlamb, I. J.; Lu, F. J.; Shaw, N. J.; Spencer, P. A.; Southgate, J. Synthesis of jaspaquinol and effect on viability of normal and malignant bladder epithelial cell lines. Bioorg. Med. Chem. Lett. 2004, 14, 2883; (f) Leahy, D. K.; Evans, P. A.; WileyVCH: Weinheim, Germany, 2005; (g) Del Bello, F.; Mattioli, L.; Ghelfi, F.; Giannella, M.; Piergentili, A.; Quaglia, W.; Cardinaletti, C.; Perfumi, M.; Thomas, R. J.; Zanelli, U.; Marchioro, C.; Dal Cin, M.; Pigini, M. Fruitful adrenergic alpha(2C)-agonism/alpha(2A)-antagonism combination to prevent and contrast morphine tolerance and dependence. J. Med. Chem. 2010, 53, 7825. (2) For selected reviews, see: (a) Katritzky, A. R.; Meth-Cohn, O.; Rees, C. W.; Elsevier Science: New York, 1995; p 4227; (b) Patai, S.; Wiley: New York, 1997; (c) Jacobsen, E. N.; Pfaltz, A.; H., Y.; Springer: New York, 1999. (3) For selected examples, see: (a) Tsuji, J.; Minami, I.; Shimizu, I. Allyation of carbonucleophiles with allylic carbonates under neutral conditions catalyzed by rhodium complexes. Tetrahedron Lett. 1984, 25, 5157; (b) Kondo, T.; Ono, H.; Satake, N.; Mitsudo, T.-a.; Watanabe, Y. Nucleophilic and Electrophilic Allylation Reactions. Synthesis, Structure, and Ambiphilic Reactivity of (.eta.3-Allyl)ruthenium(II) Complexes. Organometallics 1995, 14, 1945; (c) Takeuchi, R.; Kitamura, N. Rhodium complex35 ACS Paragon Plus Environment


Page 36 of 39

catalysed allylic alkylation of allylic acetates. New J. Chem. 1998, 22, 659; (d) Evans, P. A.; Nelson, J. D. Regioselective rhodium-catalyzed allylic alkylation with a modified Wilkinson's catalyst. Tetrahedron Lett. 1998, 39, 1725; (e) Morisaki, Y.; Kondo, T.; Mitsudo, T.-a. Ruthenium-Catalyzed Allylic Substitution of Cyclic Allyl Carbonates with Nucleophiles. Stereoselectivity and Scope of the Reaction. Organometallics 1999, 18, 4742; (f) Trost, B. M.; Fraisse, P. L.; Ball, Z. T. A Stereospecific Ruthenium-Catalyzed Allylic Alkylation. Angew. Chem. Int. Ed. 2002, 41, 1059; (g) Takeuchi, R. Iridium Complex-Catalyzed Highly Selective Organic Synthesis. Synlett. 2002, 1954; (h) Hayashi, T.; Okada, A.; Suzuka, T.; Kawatsura, M. High enantioselectivity in rhodium-catalyzed allylic alkylation of 1-substituted 2-propenyl acetates. Org. Lett. 2003, 5, 1713. (4) Bao, X.; Liu, L.; Li, J.; Fan, S. Copper-Catalyzed Oxidative Perfluoroalkylation of Aryl Boronic Acids Using Perfluoroalkylzinc Reagents. J. Org. Chem. 2018, 83, 463. (5) (a) Kato, H.; Hirano, K.; Kurauchi, D.; Toriumi, N.; Uchiyama, M. Dialkylzinc-mediated crosscoupling reactions of perfluoroalkyl and perfluoroaryl halides with aryl halides. Chem. Eur. J. 2015, 21, 3895; (b) Aikawa, K.; Nakamura, Y.; Yokota, Y.; Toya, W.; Mikami, K. Stable but reactive perfluoroalkylzinc reagents: application in ligand-free copper-catalyzed perfluoroalkylation of aryl iodides. Chem. Eur. J. 2015, 21, 96. (6) (a) Yao, T.; Hirano, K.; Satoh, T.; Miura, M. Stereospecific copper-catalyzed C-H allylation of electron-deficient arenes with allyl phosphates. Angew. Chem. Int. Ed. 2011, 50, 2990; (b) Fan, S.; Chen, F.; Zhang, X. Direct palladium-catalyzed intermolecular allylation of highly electron-deficient polyfluoroarenes. Angew. Chem. Int. Ed. 2011, 50, 5918. (7) For selected reviews, see: (a) Fried, J.; Sabo, E. F. 9α-Fluoro Derivatives of Cortisone and Hydrocortisone. J. Am. Chem. Soc. 1954, 76, 1455; (b) Shimizu, M.; Hiyama, T. Modern synthetic methods for fluorine-substituted target molecules. Angew. Chem. Int. Ed. 2005, 44, 214; (c) Mullin, R. Insights. Chem.Eng. News 2006, 84, 15; (d) Muller, K.; Faeh, C.; Diederich, F. Fluorine in pharmaceuticals: looking beyond intuition. Science 2007, 317, 1881; (e) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Fluorine in medicinal chemistry. Chem. Soc. Rev. 2008, 37, 320; (f) O'Hagan, D. Understanding organofluorine chemistry. An introduction to the C-F bond. Chem. Soc. Rev. 2008, 37, 308; (g) Wang, J.; Sanchez-Rosello, M.; Acena, J. L.; del Pozo, C.; Sorochinsky, A. E.; Fustero, S.; Soloshonok, V. A.; Liu, H. Fluorine in pharmaceutical industry: fluorine-containing drugs introduced to the market in the last decade (2001-2011). Chem. Rev. 2014, 114, 2432. (8) For selected reviews, see: (a) Zhang, C. Application of Langlois’ Reagent in Trifluoromethylation Reactions. Adv. Synth. Catal. 2014, 356, 2895; (b) Xu, J.; Liu, X.; Fu, Y. Recent advance in transitionmetal-mediated trifluoromethylation for the construction of C(sp3)–CF3 bonds. Tetrahedron Lett. 2014, 55, 585; (c) Merino, E.; Nevado, C. Addition of CF3 across unsaturated moieties: a powerful functionalization tool. Chem. Soc. Rev. 2014, 43, 6598; (d) Egami, H.; Sodeoka, M. 36 ACS Paragon Plus Environment

Page 37 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Trifluoromethylation of alkenes with concomitant introduction of additional functional groups. Angew. Chem. Int. Ed. 2014, 53, 8294; (e) Chu, L.; Qing, F. L. Oxidative trifluoromethylation and trifluoromethylthiolation reactions using (trifluoromethyl)trimethylsilane as a nucleophilic CF3 source. Acc. Chem. Res. 2014, 47, 1513; (f) Charpentier, J.; Fruh, N.; Togni, A. Electrophilic trifluoromethylation by use of hypervalent iodine reagents. Chem. Rev. 2015, 115, 650; (g) Liu, X.; Xu, C.; Wang, M.; Liu, Q. Trifluoromethyltrimethylsilane: nucleophilic trifluoromethylation and beyond. Chem. Rev. 2015, 115, 683. (9) Matsubara, S.; Mitani, M.; Utimoto, K. A facile preparation of 1-perflouroalkylalkenes and alkynes. Palladium catalyzed reaction of perfluoroalkyl iodides with organotin compounds. Tetrahedron Lett. 1987, 28, 5857. (10) (a) Kim, J.; Shreeve, J. M. The first Cu(I)-mediated nucleophilic trifluoromethylation reactions using (trifluoromethyl)trimethylsilane in ionic liquids. Organic & biomolecular chemistry 2004, 2, 2728; (b) Duan, J.-X.; Su, D.-B.; Chen, Q.-Y. Trifluoromethylation of organic halides with methyl halodifluoroacetates — a process via difluorocarbene and trifluoromethide intermediates. J. Fluorine Chem. 1993, 61, 279; (c) Chen, Q.-Y.; Duan, J.-X. Methyl 3-oxo-ω-fluorosulfonylperfluoropentanoate: a versatile trifluoromethylating agent for organic halides. J. Chem. Soc., Chem. Commun. 1993, 1389; (d) De-Bao, S.; Jian-Xiang, D.; Qing-Yun, C. Methyl chlorodifluoroacetate a convenient trifluoromethylating agent. Tetrahedron Lett. 1991, 32, 7689. (11) Xu, J.; Fu, Y.; Luo, D. F.; Jiang, Y. Y.; Xiao, B.; Liu, Z. J.; Gong, T. J.; Liu, L. Copper-catalyzed trifluoromethylation of terminal alkenes through allylic C-H bond activation. J. Am. Chem. Soc. 2011, 133, 15300. (12) Wang, X.; Ye, Y.; Zhang, S.; Feng, J.; Xu, Y.; Zhang, Y.; Wang, J. Copper-catalyzed C(sp3)-C(sp3) bond formation using a hypervalent iodine reagent: an efficient allylic trifluoromethylation. J. Am. Chem. Soc. 2011, 133, 16410. (13) Parsons, A. T.; Buchwald, S. L. Copper-catalyzed trifluoromethylation of unactivated olefins. Angew. Chem. Int. Ed. 2011, 50, 9120. (14) Chu, L.; Qing, F.-L. Copper-Catalyzed Oxidative Trifluoromethylation of Terminal Alkenes Using Nucleophilic CF3SiMe3: Efficient C(sp3)–CF3 Bond Formation. Org. Lett. 2012, 14, 2106. (15) Shimizu, R.; Egami, H.; Hamashima, Y.; Sodeoka, M. Copper-catalyzed trifluoromethylation of allylsilanes. Angew. Chem. Int. Ed. 2012, 51, 4577. (16) Kawamura, S.; Sodeoka, M. Perfluoroalkylation of Unactivated Alkenes with Acid Anhydrides as the Perfluoroalkyl Source. Angew. Chem. Int. Ed. 2016, 55, 8740. (17) (a) Albéniz, A. C.; Espinet, P.; Martín-Ruiz, B.; Milstein, D. Catalytic System for the Heck Reaction of Fluorinated Haloaryls. Organometallics 2005, 24, 3679; (b) Evans, M. E.; Burke, C. L.; Yaibuathes, S.; Clot, E.; Eisenstein, O.; Jones, W. D. Energetics of C-H bond activation of fluorinated 37 ACS Paragon Plus Environment


Page 38 of 39

aromatic hydrocarbons using a [Tp'Rh(CNneopentyl)] complex. J. Am. Chem. Soc. 2009, 131, 13464; (c) Clot, E.; Megret, C.; Eisenstein, O.; Perutz, R. N. Exceptional sensitivity of metal-aryl bond energies to ortho-fluorine substituents: influence of the metal, the coordination sphere, and the spectator ligands on M-C/H-C bond energy correlations. J. Am. Chem. Soc. 2009, 131, 7817. (18) (a) Ye, Y.; Sanford, M. S. Merging visible-light photocatalysis and transition-metal catalysis in the copper-catalyzed trifluoromethylation of boronic acids with CF3I. J. Am. Chem. Soc. 2012, 134, 9034; (b) Jiang, D.-F.; Liu, C.; Guo, Y.; Xiao, J.-C.; Chen, Q.-Y. A General, Regiospecific Synthetic Route to Perfluoroalkylated Arenes via Arenediazonium Salts with RFCu(CH3CN) Complexes. Eur. J. Org. Chem. 2014, 2014, 6303; (c) Khrizanforov, M.; Strekalova, S.; Khrizanforova, V.; Grinenko, V.; Kholin, K.; Kadirov, M.; Burganov, T.; Gubaidullin, A.; Gryaznova, T.; Sinyashin, O.; Xu, L.; Vicic, D. A.; Budnikova, Y. Iron-catalyzed electrochemical C-H perfluoroalkylation of arenes. Dalton transactions 2015, 44, 19674. (19) (a) Kamigata, N.; Ohtsuka, T.; Yoshida, M.; Shimizu, T. A Novel Perfluoroalkylation of Pyrroles with Perfluoroalkanesulfonyl chloride Catalyzed by a Ruthenium(II) Phosphine Complex. Synth. Commun. 1994, 24, 2049; (b) Kamigata, N.; Ohtsuka, T.; Fukushima, T.; Yoshida, M.; Shimizu, T. Direct perfluoroalkylation of aromatic and heteroaromatic compounds with perfluoroalkanesulfonyl chlorides catalysed by a ruthenium(II) phosphine complex. J. Chem. Soc., Perkin Trans. 1 1994, 1339. (20) Popov, I.; Lindeman, S.; Daugulis, O. Copper-catalyzed arylation of 1H-perfluoroalkanes. J. Am. Chem. Soc. 2011, 133, 9286. (21) (a) Naumann, D.; Tyrra, W.; Kock, B.; Rudolph, W.; Wilkes, B. Preparation and properties of ZnBr(CF3)·2L - a convenient route for the preparation of CF3I. J. Fluorine Chem. 1994, 67, 91; (b) Tyrra, W.; Naumann, D.; Pasenok, S. V.; Yagupolskii, Y. L. Carbenoid reactions of trifluoromethylelement compounds. Part 4. Reactions of trifluoromethylzinc bromide with enamines and methylene bases. J. Fluorine Chem. 1995, 70, 181; (c) Kremlev, M. M.; Tyrra, W.; Mushta, A. I.; Naumann, D.; Yagupolskii, Y. L. The solid complex Zn(CF3)Br·2DMF as an alternative reagent for the preparation of both, trifluoromethyl and pentafluoroethyl copper, CuCF3 and CuC2F5. J. Fluorine Chem. 2010, 131, 212. (22) Delvos, L. B.; Vyas, D. J.; Oestreich, M. Asymmetric synthesis of alpha-chiral allylic silanes by enantioconvergent gamma-selective copper(I)-catalyzed allylic silylation. Angew. Chem. Int. Ed. 2013, 52, 4650. (23) Yasuda, Y.; Ohmiya, H.; Sawamura, M. Copper-Catalyzed Enantioselective Allyl-Allyl Coupling between Allylic Boronates and Phosphates with a Phenol/N-Heterocyclic Carbene Chiral Ligand. Angew. Chem. Int. Ed. 2016, 55, 10816.


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(24) Kanayama, T.; Yoshida, K.; Miyabe, H.; Kimachi, T.; Takemoto, Y. Synthesis of beta-substituted alpha-amino acids with use of iridium-catalyzed asymmetric allylic substitution. J. Org. Chem. 2003, 68, 6197. (25) Spoehrle, S. S. M.; West, T. H.; Taylor, J. E.; Slawin, A. M. Z.; Smith, A. D. Tandem Palladium and Isothiourea Relay Catalysis: Enantioselective Synthesis of alpha-Amino Acid Derivatives via Allylic Amination and [2,3]-Sigmatropic Rearrangement. J. Am. Chem. Soc. 2017, 139, 11895. (26) Escoula, B.; Rico, I.; Laval, J. P.; Lattes, A. A New Method of Fluoroalkylation by a Wittig Reaction. Synth. Commun. 2006, 15, 35. (27) Mizuta, S.; Engle, K. M.; Verhoog, S.; Galicia-Lopez, O.; O'Duill, M.; Medebielle, M.; Wheelhouse, K.; Rassias, G.; Thompson, A. L.; Gouverneur, V. Trifluoromethylation of allylsilanes under photoredox catalysis. Org. Lett. 2013, 15, 1250.


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