Ligand-Free Iron-Catalyzed Carbon(sp2)âCarbon(sp2) Cross

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Ligand-Free Iron-Catalyzed Carbon(sp2)-Carbon(sp2) Cross-Coupling of Alkenyllithium with Vinyl halides Qiang Liu, Zhi-Yong Wang, Xiao-Shui Peng, and Henry Nai Ching Wong J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00510 • Publication Date (Web): 23 May 2018 Downloaded from http://pubs.acs.org on May 23, 2018

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The Journal of Organic Chemistry

Ligand-Free Iron-Catalyzed Carbon(sp2)-Carbon(sp2) CrossCoupling of Alkenyllithium with Vinyl halides Qiang Liu,[†] Zhi-Yong Wang,[†] Xiao-Shui Peng,*[†,§] Henry N.C. Wong*[†,§]

[†] Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, China [§] Shenzhen Municipal Key Laboratory of Chemical Synthesis of Medicinal Organic Molecules, Shenzhen Research Institute, The Chinese University of Hong Kong, No.10, Second Yuexing Road, Shenzhen 518507, China.

Email: [email protected]; [email protected]

1 ACS Paragon Plus Environment

The Journal of Organic Chemistry 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

Abstract

An efficient ligand-free iron-catalyzed cross-coupling reaction involving alkenyllithium and vinyl iodides was developed to form diene species in moderate to good yields. This new iron-catalyzed cross-coupling reaction provides a mild, inexpensive and environmentally friendly avenue towards synthesis of diversified diene derivatives.

Introduction

Transition metal-catalyzed, especially palladium-catalyzed, cross-coupling reactions of organometallic reagents with organic halides represent one of the most powerful methods in the field of carbon-carbon bond construction in the quest for structurally diverse organic molecules.1,2 Notwithstanding that Murahashi and co-workers pioneered the development of a palladium-catalyzed cross-coupling procedure making use of alkenyl halides with alkyllithium and aryllithium reagents in the 1970s,3 the use of organolithium reagents have not been considerably explored in cross-coupling reactions due to limitations such as high reactivity and low selectivity, 4 although Capriati and co-workers achieved very interesting foundation of reshaping organolithium-mediated organic transformation. 4e-4g However, the direct use of organolithium reagents as nucleophiles in cross-coupling reactions is highly desirable4c,5 because they are commercially available or easily prepared via lithium-halogen exchange or direct lithiation. It is noteworthy that organolithium compounds are usually employed as precursors to generate organomagnesium, organozinc, organotin and organoboron compounds that are used widely in metal-catalyzed cross-coupling reactions. 6 Recently, Feringa and co-workers reported elegant palladium-catalyzed cross-coupling protocols involving organolithium nucleophiles and organic halides [Figure 1(a)].7 Moreover, Feringa also disclosed for the first time palladium-based catalytic systems for alkenyllithium as cross-coupling partners [Figure 1(a)].8 On the other hand, an increasing interest has been triggered in an attempt to replace palladium with iron due to its earth-abundant, inexpensive and environmentally benign nature.9 In this context, Kochi was the first to report an iron-catalyzed crosscoupling reaction in 1971 [Figure 1(b)].10 Subsequently, Fürstner,11 Nakamura,12 Bedford13 and Cahiez14 have all contributed significantly to iron-catalyzed cross-coupling reactions.


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Figure 1. Transition metal-catalyzed cross-coupling to form carbon-carbon bonds.

Results and Discussion Recently, our group developed an efficient iron-catalyzed cross-coupling protocol under mild conditions, employing organolithium compounds and a variety of organic bromides. Our examples included formation of C(sp2)C(sp3) bonds and C(sp3)-C(sp3) bonds [Figure 1(c)].15 These approaches have therefore provided a valuable alternative to existing methodologies by showing for the first time that organolithium reagents could be employed as cross-coupling partners in iron-catalyzed cross-coupling procedures. Furthermore, our results have also prompted us to further investigate C(sp2)-C(sp2) (vinyl-vinyl) construction. Herein, we report a new catalytic protocol that allows (E)-β-aryl vinyl halides to couple with (E)-alkenyllithium reagents, resulting in moderate to good yields and with the retention of stereochemistry. The catalytic system is based on FeCl3, under a mild (0 ℃) and ligand-free condition with a short reaction time (1 h) [Figure 1(d)]. Our research began with the preliminary screening on this cross-coupling route by using (E)-propenyllithium (2a), prepared by treatment of (E)-bromopropene with elemental lithium,8 with diverse (E)-β-phenyl vinyl halides (1)16 in the presence of various commonly used iron catalysts in toluene (Table 1) or THF (see Supplementary Table S2). The most effective cross-coupling combination with high conversion (100%) and acceptable yield (52.5%) could be concluded when (E)-β-phenyl vinyl iodide (1c) was used as the cross-coupling partner in the presence of catalytic iron(III) chloride in toluene as shown in Table 1 (Entry 6). From the GC-MS spectra, polymers were detected as major by-products. To avoid this, we thereafter examined several series of NHC ligands,12a,17,18 Buchwald ligands, other commonly used phosphine-containing, amine-containing monodentate as well as bidentate ligands, and “pincer” ligands. 19 Disappointingly, none of these ligands could improve the yield (see Supplementary Tables S3.1  S3.3). Moreover, we didn’t detect any trace amount of palladium from FeCl3 using ICP-EAS analysis. In the absence of iron catalysts, the relevant control experiments were also performed, resulting in only trace amounts of cross-coupling products with major reductive by-products being formed via a fast lithium-halogen exchange.



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Table 1.Preliminary screening reactions in toluene.[a]

Entry

X

Iron catalyst

1a: Cl 1

1b: Br

59% Fe(acac)3

1c: I 1a: Cl 2

1b: Br

FeBr3

1c: I 1a: Cl 3

1b: Br

FeF2

1c: I 1a: Cl 4

1b: Br

FeF3

1c: I 1a: Cl 5

1b: Br

FeCl2

1c: I 1a: Cl 6

1b: Br

Conversion[b]

FeCl3

1c: I

Yield[b] 28%

70%

10%

83%

43.5%

24%

15%

92%

2%

Full

43%

89%

10%

42%

1%

Full

12%

23%

3%

43%

2.5%

Full

18.5%

48%

6%

43%

2%

Full

35%

65%

20%

68%

14%

Full

52.5%

[a] Initial conditions: To a solution of vinyl halides 1 (0.2 mmol) and iron catalyst (5 mol%) in toluene (1 mL) was added a solution of 2a (0.24 mmol, 1.2 eq.) in toluene (1 mL) over 1 h by a syringe pump at RT; [b] GC-MS yield of the crude reaction mixture.

Next, both (E)-1-propenyllithium (2a) and (Z)-1-propenyllithium (2b) were also examined to couple with (E)-2iodoethenylbenzene (1c) with the aim to study the stereochemistry of this cross-coupling reaction (Scheme 1). It is noteworthy that (E)-2-iodoethenylbenzene (1c) and (E)-alkenyllithium (2a) were coupled to exclusively form conjugated (E,E)-dienes (3ca) with full retention of stereochemistry, illustrating that the geometrical configurations of both vinyl iodide and alkenyllithium were fully maintained. These results were confirmed by 1H NMR spectroscopic studies and the comparison with the relevant known compound (see SI). Meanwhile, (Z)-1-propenyllithium (2b) was also examined with (E)-2-iodoethenylbenzene (1c), affording a diene mixture of [(1E,3Z)-1,3-pentadien-1-yl]benzene (3cb) and [(1E,3E)1,3-pentadien-1-yl]benzene (3ca) with an approximate ratio of 4.5 to 1,19 meaning that there was isomerization during the reaction. Scheme 1. Stereochemistry study.


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Table 2. Further optimizations based on iron(III) chloride.[a]

Entry

Equiv.

Vol. of

of 2a

Toluene

T (℃)

Conversion[a]

Yield[a]

(mL) 1

2

2

RT

Full

53%

2

1.2

4

RT

Full

63%

3

1.2

2

0

Full

66%

4

1.2

2

–20

81%

32%

5

2

2

–20

88%

35%

6

1.2

4

–20

71%

17%

7

2

4

–20

78%

21%

8

1.2

6

0

87%

56%

9

2

6

0

93%

60%

10

2

2

0

77%

67.5%

11

1.2

4

0

Full

47%

12[c]

2

4

0

Full

64.5%

13[b]

2

4

0

Full

76.5%

14[d]

2

4

0

Full

72%

[a] GC-MS yield of the crude reaction mixture; [b] Standard condition: To a solution of 1c (0.2 mmol) and FeCl3 (5 mol%, 1.6 mg) in toluene (2 mL) was added a solution of 2a (0.4 mmol) in toluene (2 mL) over 1 h by a syringe pump at 0 ℃; [c] 2a was added over 2 h; [d] 3 mol% FeCl3 was used.

With the carbon(sp2)-carbon(sp2) cross-coupling results achieved, we decided to carry out further optimization based on the aforementioned iron(III) chloride catalytic system as shown in Table 2. In order to retard the formation of polymer by-products, we first used two equivalents of the nucleophiles with the target to increase the rate of crosscoupling reaction. We also attempted to dilute the reaction concentration and lowered the reaction temperature to 0 ℃, respectively, aiming to reduce the rate of polymerization. To our delight, these three optimizations all worked out well to improve the reactions (Table 2). The results of entry 3 showed that reaction temperature at 0 ℃ could increase the reaction yield. Consequently, we reduced the reaction temperature to –20 ℃. However, the results were not encouraging (entries 4-7). In the same manner, the outcomes were also unsatisfactory when we further diluted the reaction concentration (from 2 mL to 6 mL) at room temperature (entries 8 and 9). In the case of entries 12 and 13, slow addition of 2a (2a was added in a dropwise manner over 2 hours) could also not improve the yield (entry 12). As shown in entry 13, the combination of the aforementioned factors did lead to a better reaction. Moreover, the lower loading of iron catalyst (3 mol%) was found to deduct slightly the overall transformation efficiency (entry 14).



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Table 3. Iron-catalyzed cross-coupling of (E)-β-(hetero)aryl vinyl iodides (1) with (E)-propenyllithium (2a).[a]

F

Cl

3ca 68%[e]

Br

3da 59%[e]

3ea 63%[e]

3fa 64%[e]

MeO I

F3C

3ga trace[b]

Me 3ja 61%[e]

3ia 59%[e]

3ha 63%[e]

Me

tBu Me

tBu 3ka 65%[e]

tBu 3ma trace[b]

3la 54%[e]

Me 3na 41%[c,e]

O S 3pa trace[b]

3oa 63%[e]

O 3qa 43%[e]

3ra 71%[e]

F [d,e]

3sa 40%

F F

3ta 56%[e]

[a] Conditions: To a solution of 1 (0.2 mmol) and FeCl3 (5 mol%) in toluene (2 mL) was added a solution of 2a (0.4 mmol) in toluene (2 mL) over 1 h by a syringe pump at 0 ℃; [b] GC-MS yield was less than 3%; [c] 2a (0.8 mmol) in toluene (4 mL) was added over 2h; [d] 0.8 mmol 2a (0.8 mmol) in toluene (4 mL) was added over 1 h; [e] Isolated yields.

With the optimal catalytic conditions in hand, the scope of the iron-catalyzed cross-coupling reaction of (E)propenyllithium (2a) with (E)-β-(hetero)aryl vinyl iodides (1) was further examined (Table 3). As we expected, a broad range of fluorine, chlorine and bromine substituted phenyl vinyl iodides successfully underwent the cross-coupling with an excellent chemoselectivity and moderate to good yields, affording the corresponding desired products (3da-3fa). Nevertheless, iodophenyl vinyl iodide was chemoselectively incompatible with this protocol. As can be seen, the result as detected by GC-MS was messy with a trace amount of 3ga. Vinyl iodides with both electron-deficient aromatic ring, for example the pharmaceutical useful trifluoromethylphenylvinyl iodide,20 and electron-rich aromatic ring both could smoothly underwent this coupling reaction to generate desired dienes in moderate to good yields (3ha, 3ia, 3ra). Moreover, ortho-, and para-methylphenyl-related vinyl iodides were also studied. The steric hindrance exerted by monoortho-methyl group was less obvious than that shown by di-ortho-methyl groups (3ja vs. 3na). Similarly, bulky paratertiary-butyl group has much stronger steric hindrance effect as compared with para-methyl group (3la vs. 3ka) and the more bulky di-meta-tertiary-butyl phenyl vinyl iodide only led to a trace amount of diene (3ma). It was also uncovered that the less-hindered (E)-2-(2-iodovinyl)naphthalene formed the coupling product (3oa) in 63% yield, while more sterically hindered (E)-9-(2-iodovinyl)anthracene only produced a trace amount of the desired diene (3pa). To our delight, freshly prepared (E)-β-3-thienyl vinyl iodide also successfully furnished the corresponding product (3qa). Moreover, a double coupling alkenylation product (3sa) and trifluorophenyl alkenylation product (3ta) were also obtained in 40% and 56% yields, respectively.


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Table 4. Iron-catalyzed cross-coupling of (E)-β-(hetero)aryl vinyl iodides (1) with alkenyllithiums (2c, 2d).[a]

[a] Conditions: To a solution of 1 (0.2 mmol) and FeCl3 (5 mol%) in toluene (2 mL) was added the solution of 2c or 2d (0.4 mmol) in toluene (2 mL) over 1 h by a syringe pump at 0 ℃; [b] GC yield; [c] Isolated yields.

Encouraged by these results, we envisioned to explore the electronic effect of vinyl iodides with 1-methyl-(Z)propenyllithium (2c) for this optimized coupling reaction. Gratifyingly, either electron-withdrawing/donating group substituted phenyl vinyl iodides or (E)-2-(2-iodovinyl)naphthalene and (E)-3-(2-iodovinyl)thiophene successfully underwent this cross-coupling reaction to afford the corresponding dienes in acceptable yields (Table 4, 4). Similarly, (E)-(2-(trimethylsilyl)vinyl)lithium (2d) also underwent successfully this coupling reaction with relevant vinyl iodides to form respective dienes in moderate yields (Table 4, 5). However, 1,2-dimethylpropenyllithium (2e) was not able to undergo this iron-catalyzed coupling reaction, presumably due to steric hindrance (see Supplementary Table S5). It is noteworthy that a very essential goal in the field of catalysis is to extend basic research to procedures involving scalable quantities for industrial application. Therefore, we also investigated the scale-up of our iron-catalyzed procedure to multi-gram quantities. As shown in Scheme 2, both typical gram-scale reactions smoothly provided relevant dienes in satisfactory yields in a similar procedure. Scheme 2. Gram-scale reactions.

[a] Conditions: To a solution of 1 (10 mmol) and FeCl3 (5 mol%) in toluene (100 mL) was added a solution of the corresponding 2a or 2c (20 mmol) in toluene (100 mL) over 25 h by a syringe pump at 0 ℃; [b] isolated yield.

Conclusion



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In conclusion, we have developed an efficient iron-catalyzed cross-coupling reaction involving alkenyllithium and vinyl iodides, forming useful dienes with moderate to good yields. The relevant diene products of (E)-(2(trimethylsilyl)vinyl)lithium and vinyl iodides could be conveniently converted further to other fine chemicals. Our newly developed iron-catalyzed cross-coupling reactions would provide a mild, ligand-free, inexpensive, and environmentally friendly route towards syntheses of diversified diene derivatives. To further investigate its mechanistic nature, several applications of this procedure are underway in our laboratories.

EXPERIMENTAL SECTION

General Information. All reactions were carried out under an atmosphere of dry argon with the rigid exclusion of air and moisture using standard Schlenk techniques or in a glove box unless otherwise specified. All organic solvents were freshly distilled from Na or CaH2 immediately prior to use. Analytical thin layer chromatography (TLC) was performed with Merck silica gel 60 F254 aluminum plates. Visualization was done under a UV lamp (254 nm) and by immersion in ethanolic phosphomolybdic acid (PMA) or potassium permanganate (KMnO4), followed by heating using a heat gun. Purification of crude products was generally done by preparative thin layer chromatography (PLC) with Qingdao Haiyang silica gel plates (GF254 type, 0.200.25 mm or 0.400.50 mm plate coating thickness, 200×200 mm size). For the gram-scale reactions, the purification of crude products was generally done by flash column chromatography with Grace Materials Technologies 230400 mesh silica gel. All other chemicals were purchased from Aldrich, Acros, J&K Scientific, Shaoyuan Scientific and Energy Chemical and used as received unless otherwise specified. Proton nuclear magnetic resonance spectra (1HNMR) spectra, carbon nuclear magnetic resonance spectra (13C NMR) and fluorine nuclear magnetic resonance spectra (19F NMR) were recorded at 23 °C on a Bruker DPX 400 spectrometer in CDCl3at 400 MHz for 1H, 100 MHz for

13

C and 376 MHz for

19

F.Chemical shifts (1H and

13

C) are

reported as parts per million in δ scale and referenced to the residual solvent peak (CDCl3, 7.27 ppm, 77.0 ppm respectively).Chemical shifts of 19F NMR are reported as parts per million in δ scale using fluorobenzene (113.15 ppm) or benzotrifluoride (63.72 ppm) as internal standards. Data are represented as follows: chemical shift, integration, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, dd =doublet of doublets, dq = doublet of quartets, m = multiplet, br = broad), and coupling constant (J, Hz). High resolution mass spectra (HRMS) were obtained on a Finnigan MAT 95XL GC Mass Spectrometer (Magnetic sector-double focusing) or a Thermo Scientific Q Exactive Focus Mass Spectrometer (Orbitrap). GC/MS was performed on an Agilent 7890B system (HP-5ms column) with an Agilent 5977AMSD. Preparation of (E)-β-(hetero)aryl Vinyl Halides. Aryl vinyl iodides 1c, 1d, 1f, 1h, 1i, 1j, 1k, 1o, 1r and 1s were prepared in accordance with a previously reported procedure. 16 The spectral data are in full accordance with the literature report.16 Aryl vinyl iodides 1e, 1l and 1q were prepared in accordance with a previously reported procedure. 16 The spectral data are in full accordance with the literature report, respectively. 16,21 Aryl vinyl iodide 1g, 1m, 1n and 1p were prepared in accordance with a previously reported procedure.16 Preparation of Organolithium Reagents: Method 1: (E)-propenyllithium (2a), (Z)-propenyllithium (2b) and 1-Methyl-(Z)-propenyllithium (2c).22 In a dry Schlenk flask the corresponding bromide (12.85 mmol) dissolved in diethyl ether (9 mL) was added dropwise at room temperature to a suspension of lithium shot (0.4 g) in diethyl ether (14 mL) by a syringe pump in 1.5 h. The crude organolithiums were used for cross-coupling reaction without further purification and titration. Method 2: (1E)-2-(Trimethylsilyl)ethenyllithium (2d), 1,2-Dimethyl-propenyllithium (2e).22-23 In a dry Schlenk flask the corresponding bromide (3 mmol) was dissolved in dry THF (1 mL) and the solution was cooled down to 78 ℃. tBuLi (1.3 M in pentane, 2.1 equiv, 5 mL) was added slowly and the solution was stirred for 30 min. Then the solution


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was allowed to reach room temperature and stirred for another 30 min. The crude organolithiums were used for crosscoupling reaction without further purification and titration. Iron-catalysed cross-coupling of (1E)-2-iodoethenylbenzene (1c) and (E)-propenyllithium (2a). An oven-dried test tube was equipped with a magnetic stirring bar and transferred into a glove box. FeCl3 (1.6 mg, 0.01 mmol, 5 mol%) was charged and (1E)-2-iodoethenylbenzene (1c) (0.2 mmol) and toluene (2 mL) were added subsequently. Then, the test tube was sealed properly with a rubber stopper and taken out from the glove box. At 0 ℃, (E)-propenyllithium (2a) (0.4 mmol, 0.5 M in diethyl ether, diluted with 2 mL toluene) was added by a syringe pump in 1 h. After the addition was completed, the reaction mixture was stirred at 0 ℃ for 0.5 h. Then, a saturated solution of aqueous NH4Cl was added and the aqueous layer was extracted three times with CH2Cl2.The organic phases were collected, and the solvent evaporation under reduced pressure afforded the crude product, which was then purified by preparative thin layer chromatography (pure cyclohexane). Procedure for synthesis of 1-methoxy-3-((1E,3E)-1,3-pentadien-1-yl)benzene (3ia) and 1-((1E,3E)-3-methyl-1,3pentadien-1-yl)-4-(trifluoromethyl)benzene (4hc) in a multi-gram scale. An 500 mL oven-dried round bottom flask was equipped with a magnetic stirring bar and transferred into a glove box. FeCl3 (80 mg, 0.5 mmol, 5 mol%) was charged. Then, the flask was sealed properly with a rubber stopper and taken out from the glove box. (1E)-2iodoethenyl-3-methoxybenzene (1i) and vinyl iodide (1h) (10 mmol) and toluene (100 mL) were added subsequently. The flask was transferred to 0 ℃ (ice bath), (E)-propenyllithium (2a) or 1-Methyl-(Z)-propenyllithium (2c) (20 mmol, 0.5 M in diethyl ether, diluted with 100 mL toluene) was added by a syringe pump in 25 h. After the addition was completed, the reaction mixture was stirred at 0 ℃ for 0.5 h. Then, a saturated solution of aqueous NH4Cl (100 mL) was added and the aqueous layer was extracted three times with CH2Cl2 (200 mL).The organic phases were collected, and the solvent evaporation under reduced pressure afforded the crude product, which was then purified by silica gel flash column chromatography (pure cyclohexane). 1-((E)-2-Iodoethenyl)-4-iodobenzene (1g).16 Prepared according to the general procedure and purified by preparative thin layer chromatography. Colorless oil (61% yield, 430.8 mg, 2.0 mmol scale). 1H NMR (400 MHz, CDCl3) δ 7.65 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 15.0 Hz, 1H), 7.02 (d, J = 8.3 Hz, 2H), 6.88 (d, J = 15.0 Hz, 1H).

13

C NMR (100 MHz, CDCl3)

+

δ 144.0, 137.9, 137.2, 127.7, 94.1, 77.9. HRMS m/z (ESI): calcd. for C8H6I2 [M+H] : 355.8553; found: 355.8553. 1-((E)-2-Iodoethenyl)-3,5-di-tert-butylbenzene (1m).16 Prepared according to the general procedure and purified by preparative thin layer chromatography. Colorless oil (52% yield, 355.7 mg, 2.0 mmol scale). 1H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 15.0 Hz, 1H), 7.427.41 (m, 1H), 7.18 (d, J = 1.8 Hz,2H), 6.84 (d, J = 15.0 Hz, 1H), 1.37 (s, 18H).

13

C

NMR (100 MHz, CDCl3) δ 151.3, 146.1, 137.2, 122.8, 120.5, 75.9, 35.0, 31.6. HRMS m/z (ESI): calcd. for C16H23I [M+H]+: 343.0917; found: 343.0912. 1-((E)-2-Iodoethenyl)-2,6-dimethylbenzene (1n).16 Prepared according to the general procedure and purified by preparative thin layer chromatography. Colorless oil (58% yield, 299.3 mg, 2.0 mmol scale). 1H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 15.1 Hz,1H), 7.147.10 (m, 1H), 7.067.03 (m, 2H), 6.33 (d, J = 15.0 Hz, 1H), 2.30 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 143.6, 137.7, 135.7, 128.0, 127.6, 80.4, 21.0. HRMS m/z (ESI): calcd. for C10H11I [M]+: 257.9899; found: 257.9895. 9-((E)-2-Iodoethenyl)anthracene (1p).16 Prepared according to the general procedure and purified by preparative thin layer chromatography. Colorless oil (47% yield, 310.2 mg, 2.0 mmol scale). 1H NMR (400 MHz, CDCl3) δ 8.44 (s, 1H), 8.258.20 (m, 3H), 8.01 (d, J = 8.0 Hz,2H), 7.547.46 (m, 4H), 6.69 (d, J = 15.1 Hz,1H).

13

C NMR (100 MHz, CDCl3)

δ141.9, 133.0, 131.5, 129.2, 128.7, 127.3, 126.1, 125.7, 125.5, 83.5. HRMS m/z (ESI): calcd. for C16H11I [M]+: 329.9900; found: 329.9902.



Page 10 of 17

((1E,3E)-1,3-Pentadien-1-yl)benzene (3ca).24 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Colorless oil (68% yield from 1a, 19.7 mg). 1H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 7.3 Hz, 2H), 7.30 (t, J = 7.6 Hz, 2H), 7.19 (t, J = 7.3 Hz, 1H), 6.75 (dd, J = 15.7, 10.4 Hz, 1H), 6.42 (d, J = 15.7 Hz, 1H), 6.266.19 (m, 1H), 5.83 (dq, J = 14.9, 6.8 Hz, 1H), 1.82 (d, J = 6.8 Hz, 3H).

13

C NMR (100 MHz,

CDCl3) δ 137.8, 132.0, 130.5, 129.9, 129.5, 128.7, 127.2, 126.3, 18.5. HRMS m/z (ESI): calcd. for C11H12 [M+H]+: 145.1012; found: 145.1010. 1-Fluoro-4-((1E,3E)-1,3-pentadien-1-yl)benzene (3da).25 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Colorless solid (59% yield from 1d, 19.1 mg). 1H NMR (400 MHz, CDCl3) δ 7.357.31 (m, 2H), 7.016.96 (m, 2H), 6.65 (dd, J = 15.7, 10.4 Hz, 1H), 6.38 (d, J = 15.7 Hz, 1H), 6.246.17 (m, 1H), 5.83 (dq, J = 14.9, 6.8 Hz, 1H), 1.82 (dd, J = 6.7, 1.2 Hz, 3H).13C NMR (100 MHz, CDCl3) δ 163.4, 134.0, 131.8, 130.5, 129.3, 128.6, 127.7 (d, J = 17.7 Hz), 115.6 (d, J = 21.8 Hz), 18.5.

F NMR (376 MHz, CDCl3) δ 116.4 (s, 1F).

19

+

HRMS m/z (EI): calcd. for C11H11F [M] : 162.0845; found: 162.0846. 1-Chloro-4-((1E,3E)-1,3-pentadien-1-yl)benzene (3ea).26 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow solid (63% yield from 1e, 22.4 mg). 1H NMR (400 MHz, CDCl3) δ 7.317.28 (m, 2H), 7.27 (s, 1H), 7.267.24 (m, 1H), 6.71 (dd, J = 15.7, 10.4 Hz, 1H), 6.37 (d, J = 15.7 Hz, 1H), 6.246.17 (m, 1H), 5.85 (dq, J = 14.9, 6.9 Hz, 1H), 1.82 (d, J = 6.8 Hz, 3H).

13

C NMR (100 MHz, CDCl 3) δ

136.3, 132.7, 131.7, 131.2, 130.1, 128.8, 128.5, 127.4, 18.5. HRMS m/z (EI): calcd.for C11H11Cl [M]+: 178.0544; found: 178.0545. 1-Bromo-4-((1E,3E)-1,3-pentadien-1-yl)benzene (3fa).27 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow solid (64% yield from 1f, 28.4 mg). 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.4 Hz, 2H), 6.73 (dd, J = 15.7, 10.4 Hz, 1H), 6.35 (d, J = 15.7 Hz, 1H), 6.24-6.17 (m, 1H), 5.86 (dq, J = 14.9, 6.8 Hz, 1H), 1.82 (d, J = 6.8 Hz, 3H).

13

C NMR (100 MHz, CDCl3) δ 136.8,

131.8, 131.7, 131.3, 130.2, 128.5, 127.7, 120.8, 18.6. HRMS m/z (EI): calcd.for C11H11Br [M]+: 222.0039; found: 222.0041. 1-((1E,3E)-1,3-pentadien-1-yl)-4-(trifluoromethyl)benzene (3ha).28 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). White wax-like solid (63% yield from 1h, 26.7 mg). 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 8.2 Hz, 2H), 7.45 (d, J = 8.2 Hz, 2H), 6.82 (dd, J = 15.7, 10.4 Hz, 1H), 6.43 (d, J = 15.7 Hz, 1H), 6.276.21 (m, 1H), 5.92 (dq, J = 14.9, 6.8 Hz, 1H), 1.84 (d, J = 6.7 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 141.3, 132.5, 131.9, 131.6, 129.0, 128.7, 128.3, 126.3, 125.6 (q, J = 3.7 Hz), 18.6.

F NMR (376 MHz, CDCl3) δ 62.4

19

+

(s, 3F). HRMS m/z (EI): calcd. for C12H11F3 [M] : 212.0807; found: 212.0810. 1-Methoxy-3-((1E,3E)-1,3-pentadien-1-yl)benzene (3ia). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow oil (59% yield from 1i, 35.9 mg). 1H NMR (400 MHz, CDCl3) δ 7.22 (t, J = 7.9 Hz, 1H), 6.98 (d, J = 7.6 Hz,1H), 6.92 (s, 1H), 6.786.71 (m, 2H), 6.40 (d, J = 15.7 Hz, 1H), 6.266.19 (m, 1H), 5.85 (dq, J = 14.9, 6.8 Hz, 1H), 3.82 (s, 3H), 1.83 (d, J = 6.7 Hz, 3H).

13

C NMR (100 MHz, CDCl3) δ

159.9, 139.3, 131.9, 130.7, 129.8, 129.7, 129.6, 119.0, 112.9, 111.5, 55.3, 18.5. HRMS m/z (ESI): calcd. for C12H14O [M+H]+: 175.1117; found: 175.1117. 1-Methyl-2-((1E,3E)-1,3-pentadien-1-yl)benzene (3ja). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Colorless oil (61% yield from 1j, 19.3 mg). 1H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 7.4 Hz, 1H), 7.187.11 (m, 3H), 6.676.65 (m, 2H), 6.31-6.24 (m, 1H), 5.84 (dq, J = 14.9, 6.8 Hz, 1H), 2.35 (s, 3H), 1.83 (dd, J = 6.8, 1.4 Hz, 3H).

13

C NMR (100 MHz, CDCl3) δ 136.6, 135.5, 132.4, 130.6, 130.5, 130.3,

127.5, 127.2, 126.2, 125.0, 20.0, 18.5. HRMS m/z (ESI): calcd. for C12H14 [M+H]+: 159.1168; found: 159.1168.


Page 11 of 17 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


4-Methyl-2-((1E,3E)-1,3-pentadien-1-yl)benzene (3ka).29 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). White solid (65% yield from 1k, 20.5 mg). 1H NMR (400 MHz, CDCl3) δ 7.28 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 6.72 (dd, J = 15.5, 10.2 Hz, 1H), 6.41 (d, J = 15.7 Hz, 1H), 6.266.19 (m, 1H), 5.81 (dq, J = 14.6, 7.0 Hz, 1H), 2.34 (s, 3H), 1.83 (d, J = 6.9 Hz, 3H).13C NMR (100 MHz, CDCl3) δ 137.0, 135.0, 132.1, 129.8, 129.8, 129.4, 128.5, 126.2, 21.3, 18.5. HRMS m/z (ESI): calcd. for C12H14 [M+H]+: 159.1168; found: 159.1167. 1-((1E,3E)-1,3-Pentadien-1-yl)-4-tert-butylbenzene (3la). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Colorless oil (54% yield from 1l, 21.6 mg). 1H NMR (400 MHz, CDCl3) δ 7.377.33 (m, 4H), 6.73 (dd, J = 15.6, 10.4 Hz, 1H), 6.42 (d, J = 15.7 Hz, 1H), 6.266.19 (m, 1H), 5.82 (dq, J = 14.9, 6.9 Hz, 1H), 1.83 (d, J = 6.7 Hz, 3H), 1.32 (s, 9H).13C NMR (100 MHz, CDCl3) δ 150.3, 135.0, 132.2, 129.8, 129.7, 128.8, 126.0, 125.6, 34.7, 31.4, 18.5. HRMS m/z (EI): calcd. for C15H20 [M]+: 200.1560; found: 200.1561. 2,6-Dimethyl-1-((1E,3E)-1,3-pentadien-1-yl)benzene (3na). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Colorless oil (41% yield from 1n, 14.1 mg). 1H NMR (400 MHz, CDCl3) δ 7.04 (s, 3H), 6.466.42 (m,1H), 6.286.24 (m, 2H), 5.76 (dq, J = 14.0, 6.8 Hz, 1H), 2.32 (s, 6H), 1.83 (d, J = 6.5 Hz, 3H).13C NMR (100 MHz, CDCl3) δ 137.1, 136.2, 134.8, 132.3, 129.6, 128.0, 127.9, 126.5, 21.3, 18.4. HRMS m/z (EI): calcd. for C13H16 [M]+: 172.1247; found: 172.1250. 2-((1E,3E)-1,3-Pentadien-1-yl)naphthalene (3oa).30 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow solid (63% yield from 1o, 24.4 mg). 1H NMR (400 MHz, CDCl3) δ 7.78 (t,J = 7.6 Hz, 3H), 7.72 (s,1H), 7.62 (dd,J = 8.5, 1.4 Hz,1H), 7.487.40 (m,2H), 6.90 (dd, J = 15.6, 10.4 Hz, 1H), 6.60 (d, J = 15.7 Hz, 1H), 6.336.26 (m, 1H), 5.90 (dq, J = 14.6, 6.9 Hz, 1H), 1.87 (d, J = 6.6 Hz, 3H).

13

C

NMR (100 MHz, CDCl3) δ 135.3, 133.9, 132.9, 132.1, 130.7, 130.0, 129.9, 128.3, 128.0, 127.8, 126.3, 126.0, 125.7, 123.6, 18.6. HRMS m/z (ESI): calcd. for C15H14 [M+H]+: 195.1168; found: 195.1167. 3-((1E,3E)-1,3-Pentadien-1-yl)thiophene (3qa). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow solid (43% yield from 1q, 12.9 mg). 1H NMR(400 MHz, CDCl3) δ 7.277.25 (m, 1H), 7.22 (dd, J = 5.1, 1.0 Hz,1H), 7.11 (d, J = 2.1 Hz, 1H), 6.59 (dd, J = 15.6, 10.3 Hz, 1H), 6.44 (d, J = 15.7 Hz, 1H), 6.216.13 (m, 1H), 5.79 (dq, J = 14.9, 6.9 Hz, 1H), 1.82 (dd, J = 6.7, 1.0Hz, 3H).

13

C

NMR (100 MHz, CDCl3) δ 140.5, 131.9, 129.9, 129.6, 126.0, 125.0, 124.1, 121.3, 18.5. HRMS m/z (ESI): calcd. for C9H10S [M+H]+: 151.0576; found: 151.0575. 5-((1E,3E)-1,3-Pentadien-1-yl)-1,3-Benzodioxole (3ra). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow solid (71% yield from 1r, 26.7 mg). 1H NMR (400 MHz, CDCl3) δ 6.92 (s, 1H), 6.80 (d, J = 8.0 Hz, 1H), 6.74 (d, J = 8.0 Hz,1H), 6.58 (dd, J = 15.6, 10.3 Hz, 1H), 6.34 (d, J = 15.6 Hz, 1H), 6.226.15 (m, 1H), 5.94 (s, 2H), 5.79 (dq, J = 14.9, 6.9Hz, 1H), 1.81 (d, J = 6.7Hz, 3H).

13

C NMR (100

MHz, CDCl3) δ 148.1, 147.0, 132.4, 131.9, 129.7, 129.5, 127.9, 121.0, 108.5, 105.4, 101.1, 18.5. HRMS m/z (ESI): calcd. for C12H12O2 [M+H]+: 189.0910; found: 189.0914. 1,3-Bis-((1E,3E)-1,3-pentadien-1-yl)benzene (3sa). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Colorless oil (40% yield from 1s, 16.8 mg). 1H NMR (400 MHz, CDCl3) δ 7.36 (s, 1H), 7.23 (s, 3H), 6.76 (dd, J = 15.6, 10.4 Hz, 2H), 6.41 (d, J = 15.7 Hz, 2H), 6.266.19 (m, 2H), 5.85 (dq, J = 14.9, 6.9 Hz, 2H), 1.83 (d, J = 6.7Hz, 6H).

13

C NMR (100 MHz, CDCl3) δ 138.0, 132.0, 130.6, 129.8, 129.6,

128.9, 125.0, 124.2, 18.5. HRMS m/z (ESI): calcd. for C16H18 [M+H]+: 211.1481; found: 211.1479. 1,2,3-Trifluoro-5-((1E,3E)-penta-1,3-dien-1-yl)benzene (3ta). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Yellow oil (56% yield from 1t, 22.2 mg). 1H NMR (400



Page 12 of 17

MHz, CDCl3) δ 6.976.91 (m, 2H), 6.676.61 (dd, J = 12.0 Hz, 8.0 Hz, 1H), 6.25 (d, J = 16.0 Hz, 1H), 6.226.15 (m, 1H), 5.945.85 (m, 1H), 1.83 (d, J = 4 Hz, 3H).

13

C NMR (100 MHz, CDCl3) δ 132.7, 131.6 (d, J = 2Hz), 130.9, 126.6 (t, J =

5.0 Hz, 3Hz), 109.72, 109.66, 109.6, 109.5, 18.4.

F NMR (376 MHz, CDCl3) δ 135.0 (d, J = 18.8 Hz, 3F), 162.4 (t, J

19

= 41.4 Hz, 18.8 Hz, 1F). HRMS m/z (ESI): calcd. for C11H9F3 [M+H]+: 199.0729; found: 199.0730. ((1E,3E)-3-Methyl-1,3-pentadien-1-yl)benzene (4cc).31 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Colorless oil (70% yield from 1c, 22.1 mg). 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 7.6 Hz, 2H), 7.31 (t, J = 7.6 Hz, 2H), 7.19 (t, J = 7.3 Hz, 1H), 6.82 (d, J = 16.1 Hz, 1H), 6.45 (d, J = 16.1 Hz, 1H), 5.72 (q, J = 7.0 Hz, 1H), 1.87 (s, 3H), 1.80 (d, J = 7.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 138.2, 134.9, 134.1, 128.7, 128.4, 127.0, 126.3, 125.4, 14.3, 12.2. HRMS m/z (ESI): calcd. for C12H14 [M+H]+: 159.1168; found: 159.1167. 1-((1E,3E)-3-Methyl-1,3-pentadien-1-yl)-4-(trifluoromethyl)benzene (4hc). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). White solid (69% yield from 1h, 31.2 mg). 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 8.3 Hz, 2H), 6.87 (d, J = 16.1 Hz, 1H), 6.44 (d, J = 16.1 Hz, 1H), 5.79 (q, J = 7.0 Hz, 1H), 1.87 (s, 3H), 1.82 (d, J = 7.0 Hz, 3H).

13

C NMR (100 MHz, CDCl3) δ 141.7,

136.5, 134.6, 130.3, 128.7, 128.4, 126.3, 125.8, 125.6, 125.6 (q, J = 3.8 Hz), 124.0, 123.1, 14.4, 12.2.

19

F NMR (376

MHz, CDCl3) δ 61.6 (s, 3F). HRMS m/z (ESI): calcd. for C13H13F3 [M+H]+: 227.1042; found: 227.1045. 1-Methoxy-3-((1E,3E)-3-methyl-1,3-pentadien-1-yl)benzene (4ic). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Colorless oil (69% yield from 1i, 25.9 mg). 1H NMR (400 MHz, CDCl3) δ 7.22 (t, J = 8.0 Hz,1H), 7.01 (d, J = 7.6 Hz, 1H), 6.966.94 (m, 1H), 6.80 (d, J = 16.0 Hz, 1H), 6.76 (dd, J = 8.2, 2.1 Hz, 1H), 6.42 (d, J = 16.0 Hz, 1H), 5.73 (q, J = 7.0 Hz, 1H), 3.83 (s, 3H), 1.86 (s, 3H), 1.80 (d, J = 7.0 Hz, 3H).

13

C NMR (100 MHz, CDCl3) δ 159.9, 139.7, 134.8, 134.4, 129.6, 128.6, 125.3, 119.0, 112.7, 111.5, 55.3, 14.3,

12.2. HRMS m/z (ESI): calcd. for C13H16O [M+H]+: 189.1274; found: 189.1272. 2-((1E,3E)-3-Methyl-1,3-pentadien-1-yl)naphthalene (4oc).32 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). White solid (58% yield from 1o, 24.1 mg). 1H NMR (400 MHz, CDCl3) δ 7.807.75 (m, 4H), 7.64 (d, J = 8.6 Hz, 1H), 7.477.39 (m, 2H), 6.95 (d, J = 16.0 Hz, 1H), 6.62 (d, J = 16.0 Hz, 1H), 5.78 (q, J = 7.0 Hz, 1H), 1.92 (s, 3H), 1.83 (d, J = 7.0 Hz, 3H).

13

C NMR (100 MHz, CDCl3) δ 135.7,

134.9, 134.5, 133.9, 132.8, 128.6, 128.2, 128.0, 127.8, 126.3, 126.0, 125.6, 125.5, 123.7, 14.3, 12.2. HRMS m/z (ESI): calcd. for C16H16 [M+H]+: 209.1325; found: 209.1328. 3-((1E,3E)-3-Methyl-1,3-pentadien-1-yl)thiophene (4qc). Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow solid (40% yield from 1q, 13.1 mg). 1H NMR (400 MHz, CDCl3) δ 7.30-7.26 (m, 1H), 7.257.23 (m, 1H), 7.137.12 (m, 1H), 6.67 (d, J = 16.0 Hz, 1H), 6.47 (d, J = 16.0 Hz,1H), 5.67 (q, J = 7.0 Hz, 1H), 1.83 (s, 3H), 1.78 (d, J = 7.0 Hz, 3H).

13

C NMR (100 MHz, CDCl3) δ 140.9, 134.7,

134.1, 127.7, 126.0, 125.1, 121.0, 119.8, 14.2, 12.1. HRMS m/z (ESI): calcd. for C10H12S [M+H]+: 165.0732; found: 165.0731. ((1E,3E)-4-(Trimethylsilyl)-1,3-butadien-1-yl)benzene (5cd).33 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Colorless oil (53% yield from 1c, 21.4 mg). 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 7.4 Hz, 2H), 7.32 (t, J = 7.5 Hz, 3H), 6.80 (dd, J = 15.4, 10.0 Hz, 1H), 6.69 (dd, J = 10.0, 8.0 Hz, 1H), 6.59 (d, J = 15.4 Hz, 1H), 6.01 (d, J = 17.9 Hz, 1H), 0.13 (s, 9H).

13

C NMR (100 MHz, CDCl3) δ 144.2,

137.4, 135.1, 133.0, 131.8, 128.8, 127.8, 126.7, 1.1. HRMS m/z (ESI): calcd. for C13H18Si [M]+: 202.1178; found: 202.1175.


Page 13 of 17 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


1-(Trifluoromethyl)-4-((1E,3E)-4-(trimethylsilyl)-1,3-butadien-1-yl)benzene (5hd).34 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow oil (37% yield from 1h, 20.0 mg). 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 8.3 Hz, 2H), 6.85 (dd, J = 15.6, 10.0 Hz, 1H), 6.69 (dd, J = 10.0, 8.0 Hz, 1H), 6.58 (d, J = 15.5 Hz, 1H), 6.10 (d, J = 18.1 Hz, 1H), 0.13 (s, 9H).13C NMR (100 MHz, CDCl3) δ 143.6, 140.9, 137.5, 134.1, 131.2, 129.1 (q, J = 33.0 Hz), 126.7, 125.7 (q, J = 4.0 Hz), 124.3 (q, J = 259.0 Hz), 1.21.

19

F NMR (376 MHz, CDCl3) δ 61.7 (s, 3F). HRMS m/z (ESI): calcd. for C14H17F3Si [M+H]+: 271.1124; found:

271.1124. 1-Methoxy-3-((1E,3E)-4-(trimethylsilyl)-1,3-butadien-1-yl)benzene

(5id).

Prepared

according

to

the

general

procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow oil (61% yield from 1i, 28.3 mg). 1H NMR (400 MHz, CDCl3) δ 7.23 (d, J = 7.9 Hz, 1H), 7.01 (d, J = 6.7 Hz, 1H), 6.94 (s, 1H), 6.816.79 (m, 1H), 6.76 (d, J = 10.1 Hz, 1H), 6.68 (dd, J = 10.0, 8.0 Hz, 1H), 6.55 (d, J = 15.2 Hz, 1H), 6.02 (d, J = 17.9 Hz, 1H), 3.82 (s, 3H), 0.12 (s, 9H).

13

C NMR (100 MHz, CDCl3) δ 159.9, 144.1, 138.8, 135.4, 132.9, 132.1, 129.7, 119.4, 113.5, 111.8,

55.3, 1.1. HRMS m/z (ESI): calcd. for C14H20OSi [M]+: 232.1283; found: 232.1279. 2-((1E, 3E)-4-(Trimethylsilyl)-1,3-butadien-1-yl)naphthalene (5od).35 Prepared according to the general procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow solid (59% yield from 1o, 29.7 mg). 1H NMR (400 MHz, CDCl3) δ 7.827.77 (m, 3H), 7.76 (s, 1H), 7.63 (d, J = 8.4 Hz, 1H), 6.496.41 (m, 2H), 6.93 (dd, J = 15.5, 10.0 Hz,1H), 6.78 (d, J = 8.0 Hz, 1H),6.73 (t, J = 4.9 Hz, 1H), 6.06 (d, J = 18.2 Hz, 1H), 0.15 (s, 9H).

13

C NMR

(100 MHz, CDCl3) δ 144.3, 135.4, 134.9, 133.8, 133.2, 133.1, 132.2, 128.4, 128.1, 127.8, 126.8, 126.4, 126.1, 123.7, 1.1. HRMS m/z (ESI): calcd. for C17H20Si [M]+: 252.1329; found: 252.1329.

Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI:XXXX. Experimental results for “Optimization of Reaction Conditions”, “Iron-catalyzed Cross-coupling with (Z)Propenyllithium and 1,2-Dimethyl-propenyllithium”. 1H NMR and 13C NMR spectra of compounds 3ca, 3da, 3ea, 3fa, 3ha, 3ia, 3ja, 3ka, 3la, 3na, 3oa, 3qa, 3ra, 3sa, 3ta, 4cc, 4hc, 4cc, 4oc, 4qc, 5cd, 5hd, 5id, 5od. 19F NMR spectra of compounds 3da, 3ha, 3ta, 4hc, 5hd.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] *E-mail: [email protected]

Author Contributions The manuscript was written through contributions of all authors. / All authors have given approval to the final version of the manuscript. Notes Any additional relevant notes should be placed here.

ACKNOWLEDGMENT Grants from the National Natural Science Foundation of China (NSFC Project Nos. 21672181/21272199), Shenzhen Science and Technology Innovation Committee (JCYJ20160608151520697/JCYJ20140425184428455), NSFC/RGC Joint

Research

Scheme

(N_CUHK451/13),

Research

Grants

Council


of

Hong

Kong

(GRF

Projects


403012/CUHK14309216/CUHK14303815 and CRF PolyU C5023-14G), a grant to the State Key Laboratory of Synthetic Chemistry and GHP/004/16GD from Innovation and Technology Commission, The Chinese Academy of Sciences-Croucher Foundation Funding Scheme for Joint Laboratories are gratefully acknowledged.

REFERENCES (1). Negishi, E.-i. Magical Power of Transition Metals: Past, Present, and Future (Nobel Lecture). Angew. Chem. Int. Ed. 2011, 50, 6738-6764. (b) Jana, R.; Pathak, T. P.; Sigman, M. S. Advances in Transition Metal (Pd,Ni,Fe)Catalyzed Cross-Coupling Reactions Using Alkyl-organometallics as Reaction Partners. Chem. Rev. 2011, 111, 1417-1492. (c) Terao, J.; Kambe, N. Cross-Coupling Reaction of Alkyl Halides with Grignard Reagents Catalyzed by Ni, Pd, or Cu Complexes with π-Carbon Ligand(s). Acc. Chem. Res. 2008, 41, 1545-1554. (2). (a) Johansson Seechurn, C. C. C.; Kitching, M. O.; Colacot, T. J.; Snieckus, V. Palladium-Catalyzed CrossCoupling: A Historical Contextual Perspective to the 2010 Nobel Prize. Angew. Chem. Int. Ed. 2012, 51, 50625085. (b) Wu, X.-F.; Anbarasan, P.; Neumann, H.; Beller, M. From Noble Metal to Nobel Prize: PalladiumCatalyzed Coupling Reactions as Key Methods in Organic Synthesis. Angew. Chem. Int. Ed. 2010, 49, 90479050. (c) Nicolaou, K. C.; Bulger, P. G.; Sarlah, D. Palladium-Catalyzed Cross-Coupling Reactions in Total Synthesis. Angew. Chem. Int. Ed. 2005, 44, 4442-4489. (3). (a) Murahashi, S.-I.; Yamamura, M.; Yanagisawa, K.-i.; Mita, N.; Kondo, K. Stereoselective Synthesis of Alkenes and Alkenyl Sulfides from Alkenyl Halides Using Palladium and Ruthenium Catalysts. J. Org. Chem. 1979, 44, 2408-2417. (b) Yamamura, M.; Moritani, I.; Murahashi, S.-I. The Reaction of σ-Vinylpalladium Complexes with Alkyllithiums. Stereospecific Syntheses of Olefins from Vinyl Halides and Alkyllithiums. J. Organomet. Chem. 1975, 91, C39-C42. (4). (a) Clayden, J. Organolithiums: Selectivity for Synthesis. Oxford University Press, Oxford 2002. For highlights, see: (b) Firth, J. D.; O’Brien, P. ChemCatChem 2015, 7, 395-397. (c) Pace, V.; Luisi, R. ChemCatChem 2014, 6, 1516-1519. (d) Capriati, V.; Perna, F. M.; Salomone, A. Dalton Trans. 2014, 43, 14204-14210. (e) García-Álvarez, J.; Hevia, E.; Capriati, V., Reactivity of Polar Organometallic Compounds in Unconventional Reaction Media: Challenges and Opportunities. Eur. J. Org. Chem. 2015, 2015, 6779-6799. (f) Cicco, L.; Sblendorio, S.; Mansueto, R.; Perna, F. M.; Salomone, A.; Florio, S.; Capriati, V., Water opens the door to organolithiums and Grignard reagents: exploring and comparing the reactivity of highly polar organometallic compounds in unconventional reaction media towards the synthesis of tetrahydrofurans. Chem. Sci. 2016, 7, 1192-1199. (g). Dilauro, G.; Dell'Aera, M.; Vitale, P.; Capriati, V.; Perna, F. M., Unprecedented Nucleophilic Additions of Highly Polar Organometallic Compounds to Imines and Nitriles Using Water as a Non-Innocent Reaction Medium. Angew. Chem. Int. Ed. 2017, 56, 10200-10203. (5). (a) Tao, J.-L.; Wang, Z.-X. Pincer-Nickel-Catalyzed Allyl-Aryl Coupling between Allyl Methyl Ethers and Arylzinc Chlorides. J. Org. Chem. 2016, 5, 521–527. (b) Su, B.; Cao, Z.-C.; Shi, Z.-J. Exploration of Earth-Abundant Transition Metals (Fe, Co, and Ni) as Catalysts in Unreactive Chemical Bond Activations. Acc. Chem. Res. 2015, 48, 886-896. (c) Toutov, A. A.; Liu, W.-B.; Betz, K. N.; Fedorov, A.; Stoltz, B. M.; Grubbs, R. H. Silylation of C–H Bonds in Aromatic Heterocycles by an Earth-abundant Metal Catalyst. Nature 2015, 518, 80-84. (d) deMeijere, A.; Brase, S.; Oestreich, M. Metal-Catalyzed Cross-Coupling Reactions and More, Vols. 1, 2 and 3, Wiley-VCH, Weinheim, 2014. (e) Beller, M.; Bolm, C. Transition Metals for Organic Synthesis, 2nd Ed., Wiley-VCH, Weinheim, 2004. (6). (a) Rappoport, Z.; Marek, I. The Chemistry of Organolithium Compounds, Wiley-VCH, Weinheim, 2004. (b) Luisi, R.; Capriati, V. Lithium Compounds in Organic Synthesis: From Fundamentals to Applications, Wiley-VCH, Weinheim, 2014. (7). (a) Giannerini, M.; Fañanás-Mastral, M.; Feringa, B. L. Direct Catalytic Cross-Coupling of Organolithium Compounds. Nat. Chem. 2013, 5, 667-672. (b) Vila, C.; Giannerini, M.; Hornillos, V.; Fañanás-Mastral, M.; Feringa, B. L. Palladium-Catalysed Direct Cross-Coupling of Secondary Alkyllithium Reagents. Chem. Sci. 2014,


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5, 1361-1367. (c) Vila, C.; Hornillos, V.; Giannerini, M.; Fañanás-Mastral, M.; Feringa, B. L. Palladium-Catalysed Direct Cross-Coupling of Organolithium Reagents with Aryl and Vinyl Triflates. Chem. Eur. J. 2014, 20, 1307813083. (d) Castelló, L. M.; Hornillos, V.; Vila, C.; Giannerini, M.; Fañanás-Mastral, M.; Feringa, B. L. Pd-Catalyzed Cross-Coupling of Aryllithium Reagents with 2‑Alkoxy-Substituted Aryl Chlorides: Mild and Efficient Synthesis of 3,3′-Diaryl BINOLs. Org. Lett. 2015, 17, 62-65. (e) Heijnen, D.; Hornillos, V.; Corbet, B. P.; Giannerini, M.; Feringa, B. L. Palladium-Catalyzed C(sp3)-C(sp2) Cross-Coupling of (Trimethylsilyl)methyllithium with (Hetero)Aryl Halides. Org. Lett. 2015, 17, 2262–2265. (8). Hornillos, V.; Giannerini, M.; Vila, C.; Fañanás-Mastral, M.; Feringa, B. L. Direct Catalytic Cross-Coupling of Alkenyllithium Compounds. Chem. Sci. 2015, 6, 1394-1398. (9). (a) Bauer, I.; Knölker, H.-J. Iron Catalysis in Organic Synthesis. Chem. Rev. 2015, 115, 3170-3387. (b) Bedford, R. B.; Brenner, P. B. Top. Organomet. Chem. Springer, Heidelberg, 2015. (c) Bedford, R. B. How Low Does Iron Go? Chasing the Active Species in Fe-Catalyzed Cross-Coupling Reactions. Acc. Chem. Res. 2015, 48, 14851493. (d) Kuzmina, O. M.; Steib, A. K.; Moyeux, A.; Cahiez, G.; Knochel, P. Recent Advances in Iron-Catalyzed Csp2–Csp2 Cross-Couplings. Synthesis 2015, 47, 1696-1705. (e) Nakamura,E.; Hatakeyama, T.; Ito, S.; Ishizuka, K.; Ilies, L.; Nakamura, M. Iron-Catalyzed Cross-Coupling Reactions. Org. React. 2014, 83, 1-209. (f) Sherry, B. D.; Fürstner, A. The Promise and Challenge of Iron-Catalyzed Cross Coupling. Acc. Chem. Res. 2008, 41, 15001511. (g) Plietker, B. Iron Catalysis in Organic Chemistry, Wiley-VCH, Weinheim, 2008. (10). (a) Smith, R. S.; Kochi, J. K. Mechanistic Studies of Iron Catalysis in the Cross Coupling of Alkenyl Halides and Grignard Reagents. J. Org. Chem. 1976, 41, 502-509. (b) Neumann, S. M.; Kochi, J. K. Synthesis of Olefins. Cross-Coupling of Alkenyl Halides and Grignard Reagents Catalyzed by Iron Complexes. J. Org. Chem. 1975, 40, 599-606. (c) Kochi, J. K. Electron-Transfer Mechanisms for Organometallic Intermediates in Catalytic Reactions. Acc. Chem. Res. 1974, 7, 351-360. (d) Tamura, M.; Kochi, J. K. Vinylation of Grignard Reagents (Catalysis by Iron). J. Am. Chem. Soc. 1971, 93, 1487-1489. (e) Tamura, M.; Kochi, J. K. Coupling of Grignard Reagents with Organic Halides. Synthesis 1971, 3, 303-305. (11). For recent examples, see: (a) Echeverria, P.-G.; Fürstner, A. An Iron-Catalyzed Bond-Making/Bond-Breaking Cascade Merges Cycloisomerization and Cross-Coupling Chemistry. Angew. Chem. Int. Ed. 2016, 55, 1118811192. (b) Tindall, D. J.; Krause, H.; Fürstner, A. Iron-Catalyzed Cross-Coupling of 1-Alkynylcyclopropyl Tosylates and Related Substrates. Adv. Synth. Catal. 2016, 358, 2398-2403. (c) Casitas, A.; Krause, H.; Goddard, R.; Fürstner, A. Elementary Steps of Iron Catalysis: Exploring the Links between Iron Alkyl and Iron Olefin Complexes for their Relevance in C-H Activation and C-C Bond Formation. Angew. Chem. Int. Ed. 2015, 54, 1521-1526. (d) Sun, C.-L.; Krause, H.; Fürstner, A. A Practical Procedure for Iron-Catalyzed Cross-Coupling Reactions of Sterically Hindered Aryl-Grignard Reagents with Primary Alkyl Halides. Adv. Synth. Catal. 2014, 356, 1281-1291. (12). For recent examples, see: (a) Agata, R.; Iwamoto, T.; Nakagawa, N.; Isozaki, K.; Hatakeyama, T.; Takaya, H.; Nakamura, M. Iron Fluoride/N-Heterocyclic Carbene Catalyzed Cross Coupling between Deactivated Aryl Chlorides and Alkyl Grignard Reagents with or without β-Hydrogens. Synthesis 2015, 47, 1733-1740. (b) Jin, M.; Adak, L.; Nakamura, M. Iron-Catalyzed Enantioselective Cross-Coupling Reactions of α‑Chloroesters with Aryl Grignard Reagents. J. Am. Chem. Soc. 2015, 137, 7128-7134. (c) Nakagawa, N.; Hatakeyama, T.; Nakamura, M. Iron-Catalyzed Diboration and Carboboration of Alkynes. Chem. Eur. J. 2015, 21, 4257-4261. (13). For recent examples, see: (a) Bedford, R. B.; Brenner, P. B.; Elloriaga, D.; Harvey, J. N.; Nunn, J. The Influence of the Ligand Chelate Effect on Iron-Amine-Catalysed Kumada Cross-Coupling. Dalton Trans. 2016, 45, 1581115817. (b) Bedford, R. B.; Gallagher, T.; Pye, D. R.; Savage, W. Towards Iron-Catalysed Suzuki Biaryl CrossCoupling: Unusual Reactivity of 2-Halobenzyl Halides. Synthesis 2015, 47, 1761-1765. (c) Bedford, R. B.; Brenner, P. B.; Carter, E.; Cogswell, P. M. Haddow, M. F.; Harvey, J. N.; Murphy, D. M.; Nunn, J.; Woodall, C. H. TMEDA in Iron-Catalyzed Kumada Coupling: Amine Adduct versus Homoleptic “ate” Complex Formation. Angew. Chem. Int. Ed. 2014, 53, 1804-1808.



(14). For recent examples, see: (a) Benischke, A. D.; Breuillac, A. J. A.; Moyeux, A.; Cahiez, G.; Knochel, P. Synlett. Iron-Catalyzed Cross-Coupling of Benzylic Manganese Chlorides with Aryl and Heteroaryl Halides. 2016, 27, 471476. (b) Cahiez, G.; Gager, O.; Buendia, J.; Patinote, C. Iron Thiolate Complexes: Efficient Catalysts for Coupling Alkenyl Halides with Alkyl Grignard Reagents. Chem. Eur. J. 2012, 18, 5860-5863. (c) Cahiez, G.; Foulgoc, L.; Moyeux, A. Iron-Catalyzed Oxidative Heterocoupling Between Aliphatic and Aromatic Organozinc Reagents: A Novel Pathway for Functionalized Aryl–Alkyl Cross-Coupling Reactions. Angew. Chem. Int. Ed. 2009, 48, 29692972. (15). Jia, Z.; Liu, Q.; Peng, X.-S.; Wong, H. N. C. Iron-Catalysed Cross-Coupling of Organolithium Compounds with Organic Halides. Nat. Commun. 2016, 7, 10614. (16). Pure (E)-β-(hetero)aryl vinyl halides were all prepared according to the literature: Bull, J. A.; Mousseau, J. J.; Charette, A. B. Convenient One-Pot Synthesis of (E)-β-Aryl Vinyl Halides from Benzyl Bromides and Dihalomethanes. Org. Lett. 2008, 10, 5485-5488. (17). (a) Hatakeyama, T.; Hashimoto, S.; Ishizuka, K.; Nakamura, M. Highly Selective Biaryl Cross-Coupling Reactions between Aryl Halides and Aryl Grignard Reagents: A New Catalyst Combination of N-Heterocyclic Carbenes and Iron, Cobalt, and Nickel Fluorides. J. Am. Chem. Soc. 2009, 131, 11949-11963. (b) Ghorai, S. K.; Jin, M.; Hatakeyama, T.; Nakamura, M. Cross-Coupling of Non-activated Chloroalkanes with Aryl Grignard Reagents in the Presence of Iron/N-Heterocyclic Carbene Catalysts. Org. Lett. 2012, 14, 1066-1069. (c) Hatakeyama, T.; Ishizuka, K.; Nakamura, M. Cross-Coupling Reactions Catalyzed by Iron Group Metals and N-Heterocyclic Carbenes via Nonconventional Reaction Mechanisms. J. Synth. Org. Chem. Jpn. 2011, 69, 1282-1298. (18). (a) Kawamura, S.; Nakamura, M. Ligand-Controlled Iron-Catalyzed Cross Coupling of Benzylic Chlorides with Aryl Grignard Reagents. Chem. Lett. 2013, 42, 183-185. (b) Jin, M.; Nakamura, M. Iron-Catalyzed Chemoselective Cross-Coupling of α-Bromocarboxylic Acid Derivatives with Aryl Grignard Reagents. Chem. Lett. 2011, 40, 10121014. (c) Hatakeyama, T.; Fujiwara, Y.-i.; Okada, Y.; Itoh, T.; Hashimoto, T.; Kawamura, S.; Ogata, K.; Takaya, H.; Nakamura, M. Kumada-Tamao-Corriu Coupling of Alkyl Halides Catalyzed by an Iron-Bisphosphine Complex. Chem. Lett. 2011, 40, 1030-1032. (19). (a) The ratio of stereoisomers was determined by 1H NMR spectrum and compared with those of known compounds reported in the literature (For more details, see SPI Table S4). (b). Mansueto, R.; Perna, F. M.; Salomone, A.; Florio, S.; Capriati, V., Dynamic resolution of lithiated ortho-trifluoromethyl styrene oxide and the effect of chiral diamines on the barrier to enantiomerisation. Chem. Commun. 2013, 49, 4911-4913. (c). Perna, F. M.; Salomone, A.; Dammacco, M.; Florio, S.; Capriati, V., Solvent and TMEDA effects on the configurational stability of chiral lithiated aryloxiranes. Chem. Eur. J., 2011, 17, 8216-8225. (20). Wang, J.; Sánchez-Roselló, M.; Aceña, J. L.; Pozo, C. d.; 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, 2432-2506. (21). a) P. Pawluć, G. Hreczycho, J. Szudkowska, M. Kubichi, B. Marciniec, New One-Pot Synthesis of (E)-β-Aryl Vinyl Halides from Styrenes. Org. Lett. 2009, 11, 3390-3393; b) P. S. Fier, J. F. Hartwig, Copper-Mediated Difluoromethylation of Aryl and Vinyl Iodides. J. Am. Chem. Soc. 2012, 134, 5524-5527; c) G. C. M. Lee, B. Tobias, J. M. Holmes, D. A. Harcourt, M. E. Garst, A New Synthesis of Substituted Fulvenes. J. Am. Chem. Soc. 1990, 112, 9330-9336. (22). V. Hornillos, M. Giannerini, C. Vila, M. Fañanás-Mastral, B. L. Feringa, Copper-Mediated Difluoromethylation of Aryl and Vinyl Iodides. Chem. Sci. 2012, 134, 5524-5527. (23). D. Heijnen, J.-B. Gualtierotti, V. Hornillos, B. L. Feringa, Nickel-Catalyzed Cross-Coupling of Organolithium Reagents with (Hetero)Aryl Electrophiles. Chem. Eur. J. 2016, 22, 3991-3995. (24). a) Yamashita, M.; Hirano, K.; Satoh, T.; Miura, M. Synthesis of 1,4-Diarylbuta-1,3-dienes through PalladiumCatalyzed Decarboxylative Coupling of Unsaturated Carboxylic Acids. Adv. Synth. Catal. 2011, 353, 631-636; b) Kirmse, W.; Kopannia, S. Stereochemistry of Carbenic 1,2-Vinyl Shifts. J. Org. Chem. 1998, 63, 1178-1184; c) Siddiki, S. M. A. H.; Touchy, K. A. S.; Shimizu, K. K.-i. Direct Olefination of Alcohols with Sulfones by Using


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Heterogeneous Platinum Catalysts. Chem. Eur. J. 2016, 22, 6111-6119; d) Dong, D.-J.; Li, Y.; Wang, J.-Q.; Tian, S.-K. Tunable Stereoselective Alkene Synthesis by Treatment of Activated Imines with Nonstabilized Phosphonium Ylides. Chem. Commun. 2011, 47, 2158-2160. (25). Cao, Y.; Zhang, Y.; Zhang, L.; Zhang, D.; Leng, X.; Huang, Z., Selective synthesis of secondary benzylic (Z)allylboronates by Fe-catalyzed 1,4-hydroboration of 1-aryl-substituted 1,3-dienes. Org. Chem. Front. 2014, 1, 1101-1106. (26). Sawano, T.; Ashouri, A.; Nishimura, T.; Hayashi, T. Cobalt-Catalyzed Asymmetric 1,6-Addition of (Triisopropylsilyl)-acetylene to α,β,γ,δ-Unsaturated Carbonyl Compounds. J. Am. Chem. Soc. 2012, 134, 1893618939. (27). Dombrovskii, A. V.; Ganushchak, N. I. Haloarylation of unsaturated compounds by aromatic diazo compounds. XVI. Synthesis of 1-aryl-1,3-pentadienes by arylation of piperylene. Zhurnal Obshchei Khimii, 1962, 32, 18881892. (28). Avery, T. D.; Taylor, D. K.; Tiekink, E. R. T. A New Route to Diastereomerically Pure Cyclopropanes Utilizing Stabilized Phosphorus Ylides and γ-Hydroxy Enones Derived from 1,2-Dioxines: Mechanistic Investigations and Scope of Reaction. J. Org. Chem. 2000, 65, 5531-5546. (29). a) Ranu, B. C.; Banerjee, S. Indium Triflate Catalyzed Rearrangement of Aryl-Substituted Cyclopropyl Carbinols to 1,4-Disubstituted 1,3-Butadienes. Eur. J. Org. Chem. 2006, 3012-3015; b) Ranu, B. C.; Banerjee, S.; Das, A. Catalysis by Ionic Liquids: Cyclopropyl Carbinyl Rearrangements Catalyzed by [pmim]Br under Organic Solvent Free Conditions. Tetrahedron Lett. 2006, 47, 881-884; c) Motoyoshiya, J.; Okuda, Y.; Matsuoka, I.; Hayashi, S.; Takaguchi, Y.; Aoyama, H. Tetraphenylporphine-Sensitized Photooxygenation of (E,E)- and (E,Z)-1-Aryl-1,3pentadienes Generating cis-Endoperoxides. J. Org. Chem. 1999, 64, 493-497. (30). a) Mundal, D. A.; Lutz, K. E.; Thomson, R. Stereoselective Synthesis of Dienes from N-Allylhydrazones. J. Org. Lett. 2009, 11, 465-468; b) Becker, H.; Soler, M. A.; Sharpless, K. B. Selective Asymmetric Dihydroxylation of Polyenes. Tetrahedron 1995, 51, 1345-1376. (31). Uriac, P.; Bonnic, J.; Huet, J. Obtention de derives aryl butadieniques, ortho amines ou non, par coupure carbone-azote, en milieu basique fort. Tetrahedron. 1985, 41, 5051-5060. (32). Mundal, D. A.; Lutz, K. E.; Thomson, R. J. Stereoselective Synthesis of Dienes from N-Allylhydrazones. Org. Lett. 2009, 11, 465-468. (33). Littke, A. F.; Fu, G. C. A Versatile Catalyst for Heck Reactions of Aryl Chlorides and Aryl Bromides under Mild Conditions. J. Am. Chem. Soc. 2001, 123, 6989-7000. (34). a) Szudkowska-Frątczak, J.; Marciniec, B.; Hreczycho, G.; Kubicki, M.; Pawluć, P. Ruthenium-Catalyzed Silylation of 1,3-Butadienes with Vinylsilanes. Org. Lett. 2015, 17, 2366-2369; b) Aikawa, K.; Hioki, Y.; Mikami, K. Highly Enantioselective Alkenylation of Glyoxylate with Vinylsilane Catalyzed by Chiral Dicationic Palladium(II) Complexes. J. Am. Chem. Soc. 2009, 131, 13922-13923. (35). Goh, K. K. K.; Kim, S.; Zard, S. Z. A Synthesis of (1E,3E)-TMS Dienes from Keto-Xanthates via Chugaev-Type Elimination. J. Org. Chem. 2013, 78, 12274-12279.


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