General Synthesis of Alkenyl Sulfides by Palladium-Catalyzed Thioetherification of Alkenyl Halides and Tosylates

General Synthesis of Alkenyl Sulfides by Palladium-Catalyzed Thioetherification of Alkenyl Halides and Tosylates Noelia Velasco, Cintia Virumbrales, Roberto Sanz, Samuel Suárez-Pantiga* and Manuel A. Fernández- Rodríguez* Área de Química Orgánica, Departamento de Química, Facultad de Ciencias, Universidad de Burgos Pza. Misael Bañuelos s/n, 09001-Burgos, Spain Table of Contents for the Supporting Information General Methods... S2 Control experiment and optimization... S3 Selective thioetherification of α-bromostyrene over bromobenzene... S4 General procedure for the synthesis of alkenyl sulfides 3,4 from alkenyl bromides 1... S5 Gram scale synthesis of alkenyl sulfides 3a and 3l... S15 General procedure for the synthesis of alkenyl sulfides from α-iodostyrene... S16 General procedure for the synthesis of alkenyl sulfides from alkenyl chlorides... S16 General procedure for the synthesis of alkenyl sulphides 3,4 from alkenyl tosylates... S17 Synthesis of (4-(2-bromovinyl)phenyl)(phenyl)methanone 1g... S19 1 H and 13 C NMR spectra... S21 S1

General Methods: All reactions involving air-sensitive compounds were assembled under a N 2 atmosphere in oven-dried glassware with magnetic stirring. Temperatures are reported as bath temperatures. All common reagents and solvents were obtained from commercial suppliers and used without any further purification. Solvents were dried by standard methods. Non-commercial available alkenyl halides were prepared following known procedures: α-iodostyrene, 1 α-chlorostyrene, 2 α- tosylstyrene, 3 1-(1-bromovinyl)-3-nitrobenzene 4 and ethyl 4-(2-bromovinyl)benzoate 5 TLC was performed on alumina-backed plates coated with silica gel 60 with F 254 indicator; the chromatograms were visualized by UV light (254 nm) and/or by staining with a Ce/Mo reagent, anisaldehyde or phosphomolybdic acid solution and subsequent heating. R f values refer to silica gel. Flash column chromatography was carried out on silica gel 60, 230-400 mesh. NMR spectra were measured on Varian Mercury-Plus 300 MHz and Bruker 300 MHz spectrometers. 1 H NMR spectra were recorded at 300 MHz. Chemical shifts are reported in ppm with the residual solvent resonance as the internal standard. Data are reported as follows: chemical shift, multiplicity (splitting pattern abbreviations are: s: singlet, bs: broad singlet, d: doublet, dd: doublet of doublets, ddd doublet of doublet of doublets, dq: doublet of quartets, t: triplet, tt: triplet of triplets, td: triplet of doublets, q: quartet, ap q: apparent quartet, qq: quartet of quartets, quint: quintet, ap quint: apparent quintet, m: multiplet), coupling constants (J in Hz) and integration. 13 C NMR spectra were recorded at 75.4 MHz using broadband proton decoupling and chemical shifts are reported in ppm using residual solvent peaks as reference (CDCl 3 : δ 77.16) and the multiplicities were determined by DEPT experiments. GC-MS were recorded on an Agilent 6890N/5973 Network GC System, equipped with a HP-5MS column. Low-resolution electron impact mass spectra (EI-LRMS) were obtained at 70 ev on a mass spectrometer and only the molecular ions and/or base peaks as well as significant peaks in MS are given. High-resolution mass spectrometry (HRMS) was carried out on a Micromass AutoSpec (Waters) mass spectrometer (EI as ion source) or 6545 Q-TOF (Agilent) mass spectrometer (ESI or APCI as ion source) as specified. 1 Bartoli, G.; Cipolletti, R.; Antonio, G. D.; Giovenni, R.; Lanari, S.; Marcolini, M.; Marcantoni, E.; Org. Biomol. Chem., 2010, 8, 3509 3517. 2 Murthy, K. S.; Rey, A. W.; Can. Pat. Appl. (2006), CA 2510093. 3 Liu, H.; Wei, Y.; Cai, C.; Syntlett., 2016, 27, 2378 2383. 4 Ojha, D. P.; Prabhu, K. P.; Org. Lett., 2015, 17, 18-21. 5 Jiang, Y.; Kuang, C.; Synth. Commun., 2009, 39, 4298-4308. S2

Control experiments and optimization In the following tables it is shown the influence of different parameters in the efficiency of the alkenyl sulfide forming reaction. Entry Base Cat./Ligand a Cat. (mol %) Solvent T (ºC) Yield (%) b 1 LiHMDS Pd 2 (dba) 3 /L1 1 Toluene 110 <50 2 LiHMDS Pd 2 (dba) 3 /L2 1 Toluene 110 100 3 LiHMDS Pd 2 (dba) 3 /L3 1 Toluene 110 100 4 LiHMDS Pd 2 (dba) 3 /L4 1 Toluene 110 <5 5 LiHMDS Pd 2 (dba) 3 /L5 1 Toluene 110 <5 6 LiHMDS Pd 2 (dba) 3 /L6 1 Toluene 110 <5 7 LiHMDS Pd 2 (dba) 3 /L7 1 Toluene 110 <5 8 LiHMDS Pd 2 (dba) 3 /L8 1 Toluene 90 95 (90) 9 LiHMDS Pd 2 (dba) 3 /L2 0.01 Toluene 110 100 (93) 10 LiHMDS Pd 2 (dba) 3 /L3 0.01 Toluene 110 52 (50) 11 LiHMDS Pd 2 (dba) 3 /L2 0.01 Toluene 90 46 (40) 12 LiHMDS Pd 2 (dba) 3 /L2 0.05 Toluene 90 100 (90) 13 LiHMDS Pd 2 (dba) 3 /L2 0.05 DME 90 <5 14 NaOtBu Pd 2 (dba) 3 /L2 0.05 Toluene 90 <5 15 Cs 2 CO 3 Pd 2 (dba) 3 /L2 0.05 Toluene 90 <5 16 K 3 PO 4 Pd 2 (dba) 3 /L2 0.05 Toluene 90 <5 17 LiHMDS Pd 2 (dba) 3 /L2 0.1 Toluene 70 100 (94) 18 LiHMDS Pd 2 (dba) 3 /L2 2.5 Toluene 25 100 (93) 19 LiHMDS Pd 2 (dba) 3 /L2 0.1 DME 90 <5 20 LiHMDS Pd 2 (dba) 3 /L2 0.1 Dioxane 90 <5 21 LiHMDS Pd(OAc) 2 /L2 0.01 Toluene 90 <5 22 LiHMDS Pd[P(o-tol) 3 ] 2 /L2 0.01 Toluene 90 <5 23 LiHMDS [allylpdcl] 2 /L2 0.01 Toluene 90 90 24 LiHMDS none - Toluene 90 - a L1 = Xantphos, L2 = dppf, L3 = CyPFtBu, L4 = Sphos, L5 = RuPhos, L6 = BrettPhos, L7 = XPhos, L8 = dippf. b Conversion and yield (in brackets) estimated by 1 H NMR (300 Hz) employing CH 2 Br 2 as internal standard. S3

Preparation of catalyst stock solution A (0.4 x 10 2 M): Toluene (1.0 ml) was added to a mixture of Pd 2 (dba) 3 (51364-51-3, 683345 Aldrich) (1.8 mg) and 1,1 -ferrocenediyl-bis(diphenylphosphine) (dppf) (12150-46-8, 177261 Aldrich) (2.2 mg). The resulting solution was stirred at rt for 1 min before using. Selective thioetherification of α-bromostyrene over bromobenzene. 50 l of catalyst stock solution A was adde to a mixture of α-bromostyrene 1a (1 equiv, 0.4 mmol, 49 μl) and bromobenzene (1 equiv, 0.4 mmol, 43 μl), in dry toluene (0.8mL). Then, 1-decanethiol 2a (1.1 equiv, 0.44 mmol, 80 μl) and LiHMDS (2.4 equiv, 0.96 mmol, 0.96 ml of a 1M solution in toluene) were added to the mixture and the resulting solution was stirred at 110 ºC for 24 h. After cooling down the reaction mixture to room temperature, a solution of hexane/acoet 5:1 (10 ml) was added. This reaction mixture was filtered under vacuum through a plug of celite, washed with hexane/acoet 5:1 and the solvents evaporated under reduced presure. The crude mixture was analysed by GC MS and 1 H- NMR showing complete reaction at α-bromostyrene and no evolution of bromobenzene. Purification through a plug of silica afforded pure decyl (1-phenylvinyl) sulfide 3a (103 mg, 93 % yield). S4

General procedure for the synthesis of alkenyl sulfides 3,4 from alkenyl bromides 1. The appropriate quantity of catalyst stock solution A (10 l for reactions with 0.01 mol %; 100 l for reactions with 0.1 mol %; 250 l for reactions with 0.25 mol %) or Pd 2 (dba) 3 (1.8 mg) and dppf (2.2 mg) (for reactions with 1 mol %) was added to the corresponding alkenyl bromide 1 (1 equiv, 0.4 mmol), in dry toluene (0.8 ml) and the resulting mixture was stirred under a nitrogen atmosphere for 2 min. Then, thiol 2 (1.1 equiv, 0.44 mmol) and LiHMDS (2.4 equiv, 0.96 mmol, 0.96 ml of a 1M solution in toluene; 4039-32-1, 577928 Aldrich) were added to the mixture and the resulting solution was stirred at 110 ºC until full depletion of the bromoalkene was determined by GC MS (4-24 h). After the reaction mixture was cooled down to room temperature, a solution of hexane/acoet 5:1 (10 ml) was added. This reaction mixture was filtered under vacuum through a plug of celite and washed with hexane/acoet 5:1. The filtrate was purified through a plug of silica, washed with hexane/acoet 5:1 and was concentrated to afford pure alkenyl sulfides 3 in the yields reported in Schemes 1 and 2. Decyl (1-phenylvinyl) sulfide 3a: synthesized according to the general procedure using 100 μl of stock solution A. 94% yield (104 mg). When 10 μl of stock solution A were used: 95% yield (105 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.93 (t, J = 6.1 Hz, 3H), 1.22 1.51 (m, 14H), 1.63.72 (m, 2H), 2.72 (t, J = 7.3 Hz, 2H), 5.19 (s, 1H), 5.49 (s, 1H), 7.31 7.42 (m, 3H), 7.54 7.64 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 14.3 (CH 3 ), 22.8 (CH 2 ), 28.6 (CH 2 ), 29.1 (CH 2 ), 29.3 (CH 2 ), 29.5 (CH 2 ), 29.6 (CH 2 ), 29.7 (CH 2 ), 32.0 (CH 2 ), 32.2 (CH 2 ), 110.2 (CH 2 ), 127.2 (2 x CH), 128.4 (2 x CH), 128.4 (CH), 139.9 (C), 145.4 (C). EI-LRMS m/z 276 (M +, 19), 136 (100), 103 (45). HRMS (ESI-TOF) calc d for [C 18 H 28 S+H] +, 277.1984; found, 277.1987. S5

Cyclohexyl (1-phenylvinyl) sulfide 3b: 6 synthesized according to the general procedure using 100 μl of stock solution A. 87% yield (76 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 1.21 1.45 (m, 5H), 1.41 1.56 (m, 1H), 1.71.78 (m, 2H), 1.92.00 (m, 2H), 2.86 (tt, J = 10.3, 3.7 Hz, 1H), 5.35 (s, 1H), 5.52 (s, 1H), 7.28 7.42 (m, 3H), 7.53 7.64 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 25.9 (3 x CH 2 ), 33.0 (2 x CH 2 ), 43.9 (CH), 114.0 (CH 2 ), 127.3 (2 x CH), 128.3 (CH), 128.4 (2 x CH), 140.2 (C), 144.1 (C). EI-LRMS m/z 218 (M +, 17), 136 (100). tert-butyl (1-phenylvinyl) sulfide 3c: 7 synthesized according to the general procedure using 100 μl of stock solution A. 85% yield (65 mg). Yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 1.22 (s, 9H), 5.74 (d, J = 1.3 Hz, 1H), 5.84 (d, J = 1.3 Hz, 1H), 7.27 7.39 (m, 3H), 7.61 7.68 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 31.5 (3 x CH 3 ), 46.2 (C), 125.0 (CH 2 ), 127.7 (2 x CH), 128.1 (CH), 128.2 (2 x CH), 142.2 (C), one C peak missed due to overlapping. EI-LRMS m/z 192 (M +, 16), 136 (100), 121 (51). Triisopropylsilyl (1-phenylvinyl) sulfide 3d: synthesized according to the general procedure using 100 μl of stock solution A. 86% yield (101 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 1.03 1.11 (m, 18H), 1.13 1.26 (m, 3H), 5.68 (d, J = 0.7 Hz, 1H), 5.78 (d, J = 0.7 Hz, 1H), 7.24 7.36 (m, 3H), 7.63 7.70 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 13.3 (3 x CH), 18.6 (6 x CH 3 ), 121.7 (CH 2 ), 127.4 (2 x CH), 128.0 (2 x CH), 128.0 (CH), 140.1 (C), 142.7 (C). EI-LRMS m/z 292 (M +, 5), 249 (100), 146 (93). HRMS (ESI-TOF) calc d for [C 17 H 28 OSSi+H + ] +, 309.1708; found 309.1700. 6 Ananikov, V. P.; Orlov, N. V.; Beletskaya, I. P.; Khrustalev, V. N.; Antipin, M. Y.; Timofeeva, T. V.; J. Am. Chem. Soc., 2007, 129, 7252 7253. 7 Ojima, I.; Kondo, K..; Bull. Chem. Soc. Jpn., 1973, 46, 1539 1545. S6

Phenyl (1-phenylvinyl) sulfide 3e: 8 synthesized according to the general procedure using 100 μl of stock solution A. 86% yield (73 mg). When 10 μl of stock solution A were used: 84% yield (71 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 5.35 (s, 1H), 5.71 (s, 1H), 7.20 7.41 (m, 6H), 7.41 7.49 (m, 2H), 7.63 7.74 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 116.0 (CH 2 ), 127.3 (2 x CH), 127.4 (CH), 128.4 (2 x CH), 128.6 (CH), 129.2 (2 x CH), 132.0 (2 x CH), 133.9 (C), 138.8 (C), 144.6 (C). EI-LRMS m/z 212 (M +, 100), 103 (99). p-tolyl (1-phenylvinyl) sulfide 3f: 6 synthesized according to the general procedure using 100 μl of stock solution A. 88% yield (79 mg). When 10 μl of stock solution A were used: 82% yield (74 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 2.37 (s, 3H), 5.23 (s, 1H), 5.65 (s, 1H), 7.12 7.19 (m, 2H), 7.33 7.43 (m, 5H), 7.66 7.72 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 21.2 (CH 3 ), 114.1 (CH 2 ), 127.2 (2 x CH), 128.4 (2 x CH), 128.5 (CH), 129.8 (C), 130.0 (2 x CH), 132.9 (2 x CH), 137.8 (C), 139.0 (C), 145.5 (C). EI-LRMS m/z 226 (M +, 98), 103 (100). p-methoxyphenyl (1-phenylvinyl) sulfide 3g: synthesized according to the general procedure using 100 μl of stock solution A. 89% yield (86 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 3.80 (s, 3H), 4.98 (s, 1H), 5.51 (s, 1H), 6.87 6.92 (m, 2H), 7.30 7.40 (m, 3H), 7.42 7.47 (m, 2H), 7.61 7.66 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 55.4 (CH 3 ), 111.8 (CH 2 ), 114.9 (2 x CH), 123.4 (C), 127.1 (2 x CH), 128.4 (2 x CH), 128.5 (CH), 135.7 (2 x CH), 139.1 (C), 146.7 (C), 159.9 (C). EI-LRMS m/z 242 (M +, 100), 140 (81), 121 (80), 103 (78). HRMS (ESI-TOF) calc d for [C 15 H 14 OS+H] +, 243.0838; found, 243.0835. 8 Cao, C.; Fraser, L. R.; Love, J. A.; J. Am. Chem. Soc., 2005, 127, 17614 17615. S7

o-methoxyphenyl (1-phenylvinyl) sulfide 3h: synthesized according to the general procedure using 100 μl of stock solution A. 87% yield (84 mg). When 10 μl of stock solution A were used: 81% yield (78 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 3.89 (s, 3H), 5.32 (s, 1H), 5.69 (s, 1H), 6.82 6.91 (m, 2H), 7.19 7.39 (m, 5H), 7.64 7.72 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 56.0 (CH 3 ), 111.0 (CH 2 ), 116.1 (CH), 121.2 (CH), 122.2 (C), 127.2 (2 x CH), 128.3 (2 x CH), 128.5 (CH), 128.9 (CH), 133.2 (CH), 138.9 (C), 143.3 (C), 158.0 (C). EI-LRMS m/z 242 (M +, 100), 121 (83), 103 (83). HRMS (ESI-TOF) calc d for [C 15 H 14 OS+H] +, 243.0838; found, 243.0851. o-aminophenyl (1-phenylvinyl) sulfide 3i: synthesized according to the general procedure using 100 μl of stock solution A. 55% yield (50 mg). Brown oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 4.37 (bs, 2H), 5.82 (d, J = 2.0 Hz, 1H), 6.16 (d, J = 2.0 Hz, 1H), 6.63 (td, J = 7.5, 1.3 Hz, 1H), 6.74 (dt, J = 7.1, 1.4 Hz, 1H), 7.17 7.25 (m, 2H), 7.31.45 (m, 3H), 7.61 7.69 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 115.3 (CH), 117.7 (CH 2 ), 118.3 (CH), 126.1 (C), 127.3 (2 x CH), 128.3 (2 x CH), 129.1 (CH), 131.0 (C), 131.6 (CH), 136.7 (CH), 138.6 (C), 148.7 (C). EI-LRMS m/z 227 (M +, 15), 211 (100), 103 (100). HRMS (ESI-TOF) calc d for [C 14 H 13 NS+H] +, 228.0841; found, 228.0839. o-fluorophenyl (1-phenylvinyl) sulfide 3j: synthesized according to the general procedure using 100 μl of stock solution A. 79% yield (73 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 5.31 (s, 1H), 5.66 (s, 1H), 7.01 7.11 (m, 2H), 7.20 7.42 (m, 5H), 7.62 7.66 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 115.7 (CH 2 ), 116.0 (CH, J C-F = 22.4 Hz), 124.7 (CH, J C-F = 3.8 Hz), 127.3 (2 x CH), 128.4 (2 x CH), 128.7 (CH), 129.9 (CH, J C-F = 7.9 Hz), 134.7 (CH, J C-F = 1.1 Hz), 138.6 (C), S8

143.3 (C, J C-F = 0.9 Hz), 161.7 (C, J C-F = 247.5 Hz), one C missed due to overlapping. EI-LRMS m/z 230 (M +, 70), 103 (100). HRMS (ESI-TOF) calc d for (C 14 H 11 FS) +, 230.0560; found, 230.0559. o-chlorophenyl (1-phenylvinyl) sulfide 3k: synthesized according to the general procedure using 100 μl of stock solution A. 78% yield (77 mg). Yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 5.55 (d, J = 1.2 Hz, 1H), 5.87 (d, J = 1.2 Hz, 1H), 7.09 7.12 (m, 2H), 7.27 7.40 (m, 5H), 7.67 7.70 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 119.5 (CH 2 ), 127.2 (2 x CH), 127.3 (CH), 127.9 (CH), 128.5 (2 x CH), 128.7 (CH), 129.82 (CH), 132.2 (CH), 133.8 (C), 134.5 (C), 138.2 (C), 142.1 (C). EI-LRMS m/z 246 (M +, 44), 211 (100). HRMS data could not be obtained due to decomposition. o-bromophenyl (1-phenylvinyl) sulfide 3l: synthesized according to the general procedure using 100 μl of stock solution A. 95% yield (111 mg). When 10 μl of stock solution A were used: 87% yield (101 mg). Brown oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 5.58 (d, J = 0.5 Hz, 1H), 5.90 (d, J = 0.5 Hz, 1H), 6.99 7.05 (m, 1H), 7.11 7.16 (m, 1H), 7.35 7.36 (m, 4H), 7.57 (dd, J = 7.9, 1.3 Hz, 1H), 7.68 7.71 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 119.5 (CH 2 ), 124.6 (C), 127.18 (2 x CH), 127.7 (CH), 127.9 (CH), 128.5 (2 x CH), 128.7 (CH), 131.9 (CH), 133.1 (CH), 136.0 (C), 138.1 (C), 142.3 (C). EI-LRMS m/z 292 [(M+2) +, 23], 290 (M +, 23), 211 (100). HRMS (ESI-TOF) calc d for [C 14 H 11 BrS+H] +, 290.9838; found, 290.9834. Mesityl (1-phenylninyl) sulfide 3m: synthesized according to the general procedure using 100 μl of stock solution A. 98% yield (101 mg). Yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 2.33 (d, J = 2 Hz, 3H), 2.49 (d, J = 2.6 Hz, 6H), 4.30 (d, J = 2.9 Hz, 1H), 5.22 (d, J = 2.8 Hz, 1H), 7.02 (d, J = 0.5 Hz, 2H), 7.36 7.40 (m, 3H), 7.64 7.68 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 21.3 (CH 3 ), 21.4 (2 x CH 3 ), 106.2 (CH 2 ), 126.8 (2 x CH), 128.5 (2 x CH), 128.6 (CH), 129.0 (C), 129.4 (2 x CH), 139.4 (C), S9

139.5 (C), 143.6 (2 x C), 144.5 (C). EI-LRMS m/z 254 (M +, 51), 239 (100). HRMS (ESI-TOF) calc d for [C 17 H 18 S+H] +, 255.1202; found, 255.1204. 1-Phenylvinyl pyridin-2-yl sulfide 3n: synthesized according to the general procedure using 100 μl of stock solution A. 75% yield (64 mg). Brown oil; Rf = 0.22 (hexane/etoac = 10/1). 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 5.92 (s, 1H), 6.02 (s, 1H), 6.94 (ddd, J = 7.4, 4.9, 1 Hz, 1H), 7.04 (d, J = 8.1 Hz, 1H), 7.26 7.36 (m, 3H), 7.37 7.39 (m, 1H), 7.66 7.70 (m, 2H), 8.36 8.39 (m, 1H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 120.2 (CH 2 ), 123.0 (CH), 123.2 (CH), 127.3 (2 x CH), 128.5 (2 x CH), 128.7 (CH), 136.6 (CH), 138.5 (C), 140.8 (C), 149.8 (CH), 159.2 (C). EI-LRMS m/z 212 (M +, 100), 77 (12). HRMS (ESI-TOF) calc d for [C 13 H 11 NS+H] +, 214.0685; found, 214.0690. 1-Phenylvinyl thiophen-2-yl sulfide 3o: synthesized according to the general procedure using 100 μl of stock solution A. 77% yield (67 mg). Brown oil; Rf = 0.34 (hexane/etoac = 10/1). 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 4.99 (s, 1H), 5.48 (s, 1H), 7.05 (dd, J = 5.3, 3.6 Hz, 1H), 7.25 (dd, J = 3.6, 1.2 Hz, 1H), 7.36 7.33 (m, 3H), 7.46 (dd, J = 5.4, 1.3 Hz, 1H), 7.61 7.57 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 111.4 (CH 2 ), 127.1 (2 x CH), 127.9 (CH), 128.4 (2 x CH), 128.7 (CH), 131.3 (CH), 136.1 (CH), 138.4 (C), 146.9 (C), one C peak missed due to overlapping. EI-LRMS m/z 218 (M +, 55), 103 (100). HRMS data could not be obtained due to decomposition. Decyl (2-phenylvinyl) sulfide 4a synthesized according to the general procedure using 250 μl of stock solution A. 87% yield (96 mg). Mixture diastereoisomers E/Z ca. 10:1 (equivalent mixture as the starting alkenyl bromide). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.89 (t, J = 6.5 Hz, 3H), 1.21 1.50 (m, 14H), 1.70 (quint, J = 7.3 Hz, 2H), 2.81 (t, J = 7.3 Hz, 2H), 6.47 (d, J =15.6 Hz, 1H), 6.74 (d, J =15.6 Hz, 1H), 7.15 7.24 (m, 1H), 7.27 7.33 (m, 4H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 14.3 (CH 3 ), 22.8 (CH 2 ), 29.0 (CH 2 ), 29.3 (CH 2 ), 29.5 (CH 2 ), 29.6 (CH 2 ), 29.7 (CH 2 ), 29.7 S10

(CH 2 ), 32.0 (CH 2 ), 32.7 (CH 2 ), 125.4 (CH), 125.5 (2 x CH), 126.7 (CH), 126.8 (CH), 128.7 (2 x CH), 137.3 (C). EI-LRMS m/z 276 (M +, 100), 136 (61), 91 (26). Phenyl (2-phenylvinyl) sulfide 4b: 9 synthesized according to the general procedure using 250 μl of stock solution A. 91% yield (77 mg). Mixture diastereoisomers E/Z 10:1 (equivalent mixture as the starting alkenyl bromide). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 6.84 (d, J = 15.5 Hz, 1H), 6.99 (d, J = 15.5 Hz, 1H), 7.27 7.71 (m, 10H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 123.5 (CH), 126.1 (2 x CH), 127.1 (CH), 127.7 (CH), 128.8 (2 x CH), 129.3 (2 x CH), 129.9 (2 x CH), 131.9 (CH), 135.4 (C), 136.6 (C). EI-LRMS m/z 212 (M +, 100), 178 (41). o-bromophenyl (2-phenylvinyl) sulfide 4c: 10 synthesized according to the general procedure using 250 μl of stock solution A. 84% yield (98 mg). Mixture diastereoisomers E/Z 10:1 (equivalent mixture as the starting alkenyl bromide). Brown oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 6.86 (d, J = 15.3 Hz, 1H), 6.97 (d, J = 15.4 Hz, 1H), 7.08 7.62 (m, 8H), 7.60 (d, J = 7.9 Hz, 1H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 120.7 (CH), 122.8 (C), 126.3 (2 x CH), 127.4 (CH), 127.9 (CH), 128.2 (CH), 128.8 (2 x CH), 129.0 (CH), 133.0 (CH), 135.5 (CH), 136.1 (C), 137.6 (C). EI-LRMS m/z 292 [(M+2) +, 30], 290 (M +, 30),292 (M +, 30), 149 (100). Triisopropylsilyl (2-phenylvinyl) sulfide 4d: synthesized according to the general procedure using 250 μl of stock solution A. 88% yield (103 mg). Mixture diastereoisomers E/Z 10:1 (equivalent mixture as the starting alkenyl bromide). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 1.18 1.26 (m, 18H), 1.32 1.46 (m, 3H), 6.76 (d, J = 15.2 Hz, 1H), 6.87 (d, J = 15.2 Hz, 1H), 7.20 7.28 (m, 1H), 7.28 7.38 (m, 4H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 12.9 (3 x CH), 18.5 (6 x CH 3 ), 119.3 (CH), 125.6 (2 x CH), 127.1 (CH), 128.7 (2 x CH), 134.7 (CH), 137.4 (C). EI-LRMS m/z 292 (M +, 85), 249 (100). HRMS calc d for [C 17 H 28 SSi+H] +, 293.1754; found, 293.1745. 9 Taniguchi, T.; Fujii, T.; Idota, A.; Ishibashi, H.; Org. Lett., 2009, 11, 3298-3301. 10 Lin, Y.; Lu, G.; Wang, G.; Yi, W.; J. Org. Chem., 2017, 82, 382-389. S11

[1-(3-Nitrophenyl)vinyl] phenyl sulfide 4e: synthesized according to the general procedure using 250 μl of stock solution A and using 1.1 equiv of LiHMDS (0.44 mmol, 0.44 ml of a 1M solution in toluene). Compound 4e was purified through flash column chromatography on silica gel (Hexane: Hexane:EtOAc 10:1 to 4:1, Rf = 0.25 Hexane: EtOAc 10:1) affording 101 mg as mixture 1:0.7 4e:EtOAc (70% yield). Neat samples of 4e decomposed within minutes, particularly fast when exposed to light, whereas ethyl acetate stock solutions could be stored for few days. Yellow oil. 1 H NMR (300 MHz, CD 3 COCD 3, 25 ºC) δ = 5.63 (s, 1H), 6.01 (s, 1H), 7.25 7.38 (m, 3H), 7.40 7.49 (m, 2H), 7.61 7.72 (m, 1H), 8.09 (ddd, J = 7.8, 1.8, 1.0 Hz, 1H), 8.18 (ddd, J = 8.2, 2.3, 1.0 Hz, 1H), 8.47 (t, J = 2.0 Hz, 1H) ppm. 13 C NMR (75.4 MHz, CD 3 COCD 3 ) δ = 119.5 (CH 2 ), 121.7 (CH), 123.2 (CH), 127.4 (C), 127.8 (CH), 129.4 (2 x CH), 129.8 (CH), 131.6 (2 x CH), 132.8 (CH), 133.3 (C), 140.4 (C), 142.1 (C) ppm. EI-LRMS m/z 257 (M +, 100), 166 (90). HRMS data could not be obtained due to decomposition. [1-(4-Cyanophenyl)vinyl] phenyl sulfide 4f: synthesized according to the general procedure using 250 μl of stock solution A and using 1.1 equiv of LiHMDS (0.44 mmol, 0.44 ml of a 1M solution in toluene). 84% yield (80 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 5.51 (s, 1H), 5.76 (s, 1H), 7.23 7.33 (m, 3H), 7.34 7.40 (m, 2H), 7.57 7.64 (m, 2H), 7.69 7.75 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 112.0 (C), 118.6 (C), 118.9 (CH 2 ), 127.8(CH), 127.9 (2 x CH), 129.3 (2 x CH), 131.9 (2 x CH), 132.2 (2 x CH), 132.8 (C), 143.2 (C), 143.3 (C). EI-LRMS m/z 237 (M +, 98), 115 (100). HRMS (ESI-TOF) calc d for [C 15 H 11 NS+H] +, 238.0685; found, 238.0689. Decyl 2-(4-phenylcarbonylphenyl)vinyl sulfide 4g: synthesized according to the general procedure in the presence of Pd 2 (dba) 3 (1.8 mg) and CyPFtBu (2.2 mg) (1 mol %) and using Cs 2 CO 3 (2.0 equiv, 0.8 mmol, 261 mg) as base. 72% yield (110 mg). Pale yellow oil. Mixture of diastereoisomers Z/E 9:1 (equivalent mixture to the starting alkenyl bromide). The reported data correspond to the major isomer. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.75 1.00 (m, 3H), 1.14 1.56 (m, 14H), 1.62 1.85 (m, 2H), S12

2.79 2.94 (m, 2H), 6.43 6.58 (m, 2 H), 7.46 7.55 (m, 2H), 7.55 7.68 (m, 3H), 7.72 7.90 (m, 4H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 14.1 (CH 3 ), 22.7 (CH 2 ), 28.8 (CH 2 ), 29.2 (CH 2 ), 29.3 (CH 2 ), 29.5 (CH 2 ), 29.6 (CH 2 ), 30.3 (CH 2 ), 31.9 (CH 2 ), 36.2 (CH 2 ), 124.1 (CH), 128.3 (2 x CH), 129.5 (CH), 130.0 (2 x CH), 130.3 (2 x CH), 130.9 (CH), 131.4 (CH), 132.2 (CH), 135.1 (C), 137.9 (C), 141.3 (C), 196.1 (C). EI-LRMS m/z 380 (M +, 100), 105 (30). HRMS (ESI-TOF) calc d for [C 25 H 32 OS+H] +, 381.2247; found, 381.2243. 2-(4-Ethoxycarbonylphenyl)vinyl decyl sulfide 4h: synthesized according to the general procedure in the presence of Pd 2 (dba) 3 (1.8 mg) and CyPFtBu (2.2 mg) (1 mol %) and using Cs 2 CO 3 (2.0 equiv, 0.8 mmol, 261 mg) as base. 60% yield (84 mg). Pale yellow oil. Mixture of diastereoisomers Z/E 4:1 (from a 7:1 mixture of the starting alkenyl bromide). The reported data correspond to the major isomer. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.84 1.00 (m, 3H), 1.25 1.50 (m, 17H), 1.66 1.81 (m, 2H), 2.74 2.91 (m, 2H), 4.31 4.50 (m, 2H), 6.38 6.53 (m, 2H), 7.30 7.43 (m, 1H), 7.50 7.59 (m, 1H), 7.95 8.09 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 14.1 (CH 3 ), 14.4 (CH 3 ), 22.7 (CH 2 ), 28.5 (CH 2 ), 29.2 (CH 2 ), 29.3 (CH 2 ), 29.5 (CH 2 ), 29.5 (CH 2 ), 30.3 (CH 2 ), 31.9 (CH 2 ), 36.1 (CH 2 ), 60.8 (CH 2 ), 124.2 (CH), 125.1 (CH), 128.1 (C), 128.3 (2 x CH), 129.5 (2 x CH), 141.5 (C), 166.5 (C). EI-LRMS m/z 348 (M +, 100), 135 (20). HRMS (ESI-TOF) calc d for [C 21 H 32 O 2 S+H] +, 349.2196; found, 349.2196. But-2-en-2-yl decyl sulfide 4i: synthesized according to the general procedure using 250 μl of stock solution A. 81% yield (74 mg). Mixture of diastereoisomers E/Z 1:1 (equivalent mixture to the starting alkenyl bromide). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.88 (t, J = 6.5 Hz, 6H), 1.20 1.46 (m, 28H), 1.47 1.63 (m, 4H), 1.64 1.70 (m, 3H), 1.73 (dq, J = 6.6, 1.5 Hz, 3H), 1.86 (ap quint, J = 1.3 Hz, 3H), 1.98 (ap quint, J = 1.5 Hz, 3H), 2.60 2.67 (m, 4H), 5.45 (qq, J =6.8, 1.3 Hz, 1H), 5.57 (qq, J =6.7, 1.5 Hz, 1H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 14.2 (3 x CH 3 ), 14.4 (CH 3 ), 15.1 (CH 3 ), 17.7 (CH 3 ), 22.8 (2 x CH 2 ), 23.7 (CH 2 ), 28.9 (CH 2 ), 29.10 (CH 2 ), 29.12 (CH 2 ), 29.4 (2 x CH 2 ), 29.5 (2 x CH 2 ), 29.67 (CH 2 ), 29.69 (2 x CH 2 ), 30.3 (CH 2 ), 30.8 (CH 2 ), 31.3 (CH 2 ), 32.0 (2 x CH 2 ), 121.0 (CH), 125.2 (CH), 129.8 (C), 130.3 (C). EI-LRMS m/z 228 (M +, 26), 88 (100). HRMS (ESI-TOF) calc d for [C 14 H 28 S+H] +, 229.1984; found, 229.1982. S13

(1-H-inden-1-yl)phenyl sulfide 4j: 11 synthesized according to the general procedure in the presence of Pd 2 (dba) 3 (1.8 mg) and dppf (2.2 mg) (1 mol %) and using 1.2 equiv of LiHMDS (0.48 mmol, 0.48 ml of a 1M solution in toluene). 87% yield (79 mg). Brown oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 3.49 (d, J = 0.6 Hz, 2H), 6.71 (s, 1H), 7.13 7.18 (m, 1H), 7.22 7.26 (m, 2H), 7.34 7.41 (m, 4H), 7.53 (dd, J = 8, 1.5 Hz, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 42.1 (CH 2 ), 102.1 (CH), 123.4 (CH), 124.4 (CH), 126.7 (CH), 127.9 (CH), 129.2 (2 x CH), 130.9 (CH), 132.4 (2 x CH), 134.0 (C), 142.2 (C), 143.3 (C), 144.6 (C). EI-LRMS m/z 224 (M +, 98), 115 (100). 3-Methylbut-2-en-2-yl decyl sulfide 4k: synthesized according to the general procedure using 250 μl of stock solution A. 86% yield (83 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.87 (t, J = 6.5 Hz, 3H), 1.23 1.41 (m, 14H), 1.44 1.54 (m, 2H), 1.74 (s, 3H), 1.91 (bs, 3H), 1.94 (bs, 3H), 2.59 (t, J =7.2 Hz, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 14.2 (CH 3 ), 19.4 (CH 3 ), 21.3 (CH 3 ), 22.8 (CH 3 + CH 2 ), 28.9 (CH 2 ), 29.4 (CH 2 ), 29.5 (CH 2 ), 29.7 (2 x CH 2 ), 30.1 (CH 2 ), 31.9 (CH 2 ), 32.0 (CH 2 ), 121.5 (C), 134.0 (C). EI-LRMS m/z 242 (M +, 100), 102 (98). HRMS (ESI-TOF) calc d for [C 15 H 30 S+H] +, 243.2141; found, 243.2133. 3-Methylbut-2-en-2-yl phenyl sulfide 4l: 12 synthesized according to the general procedure in the presence of Pd 2 (dba) 3 (1.8 mg) and dppf (2.2 mg) (1 mol %). 92% yield (66 mg). Yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 1.94 (bs, 3H), 2.01 (bs, 3H), 2.08 (bs, 3H), 7.15 7.24 (m, 1H), 7.29 7.42 (m, 4H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 20.8 (CH 3 ), 21.4 (CH 3 ), 23.4 (CH 3 ), 120.5 (C), 125.4 (CH), 128.4 (2 x CH), 128.9 (2 x CH), 136.9 (C), 139.6 (C). EI-LRMS m/z 178 (M +, 100), 110 (33). 11 Bunnett, J. F.; Creary, X; Sundberg, J. E.; J. Org. Chem., 1976, 41, 1707-1709. 12 Stensaas, K. L.; McCarty, B. V.; Touchette, N. M.; Brock, J. B.; Tetrahedron Lett., 2006, 62, 10683-10687. S14

Decyl (1,2,2-triphenylvinyl) sulfide 4m: synthesized according to the general procedure in the presence of Pd 2 (dba) 3 (1.8 mg) and dppf (2.2 mg) (1 mol %). 83% yield (142 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.91 (t, J = 6.7 Hz, 3H), 1.09 1.38 (m, 14H), 1.42 1.49 (m, 2H), 2.25 (t, J = 7.3 Hz, 2H), 6.88 6.96 (m, 2H), 6.99 7.06 (m, 3H), 7.16 7.24 (m, 3H), 7.27 7.44 (m, 7H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 14.3 (CH 3 ), 22.8 (CH 2 ), 28.8 (CH 2 ), 29.2 (CH 2 ), 29.4 (CH 2 ), 29.6 (CH 2 ), 29.7 (CH 2 ), 30.2 (CH 2 ), 32.0 (CH 2 ), 32.2 (CH 2 ), 126.2 (CH), 126.9 (CH), 127.2 (CH), 127.6 (2 x CH), 128.1 (2 x CH), 128.2 (2 x CH), 130.1 (2 x CH), 130.7 (2 x CH), 130.9 (2 x CH), 136.3 (C), 139.1 (C), 142.2 (C), 142.8 (C), 143.9 (C). EI-LRMS m/z 428 (M +, 100), 287 (75). HRMS (ESI-TOF) calc d for [C 30 H 36 S+H] +, 429.2610; found, 429.2608. Gram scale synthesis of alkenyl sulfides 3a and 3l. A solution of α-bromostyrene 1a (1 equiv, 7 mmol, 0.85 ml), Pd 2 dba 3 (0.005 mol%, 0.00035 mmol, 0.32 mg) and 1,1 -ferrocenediyl-bis(diphenylphosphine) (dppf) (0.01 mol%, 0.0007 mmol, 0.4 mg) in dry toluene (14 ml) was allowed to stir under a nitrogen atmosphere for 2 min. Then, 1-decanethiol 2a (1.1 equiv, 7.7 mmol, 1.40 ml) or 2-bromothiophenol 2l (1.1 equiv, 7.7 mmol, 0.83 ml) and LiHMDS (2.4 equiv, 16.8 mmol, 16.8 ml of a 1M solution in toluene) were added to the mixture and the resulting solution was stirred at 110 ºC until full depletion of the bromoalkene was determined by GC MS (4-24 h). After the reaction mixture was allowed to cool down to room temperature, a solution of hexane/acoet 5:1 (10 ml) was added and the reaction mixture was filtered under vacuum through a plug of celite and washed with hexane/acoet 5:1. The filtrate was purified through a plug of silica, washed with hexane/acoet 5:1. The filtrate was concentrated affording pure decyl (1-phenylvinyl) sulfide 3a (1.86 g, 95 % yield) or o-bromophenyl (1-phenylvinyl) sulfide 3l (1.78 mg, 87 % yield). S15

General procedure for the synthesis of alkenyl sulfides from α-iodostyrene. The appropriate quantity of catalyst stock solution A (10 l for reaction with 0.01 mol %; 50 l for reaction with 0.05 mol %) was added to a solution of synthesize α-iodostyrene 1 (1 equiv, 0.4 mmol, 92 mg) in dry toluene (0.8 ml) and the resulting mixture was stirred under a nitrogen atmosphere for 2 min. Then, thiophenol or 1-decanethiol (1.1 equiv, 0.44 mmol, 45 µl and 91 µl respectively) and LiHMDS (2.4 equiv, 0.96 mmol, 0.96 ml of a 1M solution in toluene) were added to the reaction mixture and the resulting solution was stirred at 110 ºC until full depletion of α-iodostyrene was determined by GC MS (4-24 h). After that, the reaction mixture was allowed to cool down to room temperature and a solution of hexane/acoet 5:1 (10 ml) was added. The reaction mixture was filtered under vacuum through a plug of celite and washed with hexane/acoet 5:1. The filtrate was purified through a plug of silica and washed with hexane/acoet 5:1. The filtrate was concentrated affording pure decyl (1-phenylvinyl) sulfide 3a (100 mg, 91 % yield) or phenyl (1-phenylvinyl) sulfide 3e (60 mg, 72 % yield). General procedure for the synthesis of alkenyl sulfides from alkenyl chlorides: A solution of α-chlorostyrene 2 or 1-chlorocyclopentene (1 equiv, 0.4 mmol, 92 mg and 39.6 µl respectively), Pd 2 dba 3 (0.25 mol%, 0.001 mmol, 1.0 mg or 0.5 mol %, 0.002 mmol, 1.8 mg), CyPFtBu (0.5 mol%, 0.002 mmol, 1.1 mg or 1 mol%, 0.004 mmol, 2.2 mg) in dry toluene (0.8 ml) was stirred under a nitrogen atmosphere for 2 min. Then, thiophenol or 1-decanethiol (1.1 equiv, 0.44 mmol, 45 µl or 91 µl respectively) and LiHMDS (2.4 equiv, 0.96 mmol, 0.96 ml of a 1M solution in toluene) were added to the mixture and the resulting solution was stirred at 110 ºC for 24 h. After that, the reaction mixture was allowed to cold down to room temperature and a solution of hexane/acoet 5:1 (10 ml) was added. The reaction mixture was filtered under vacuum through a plug of celite and washed with hexane/acoet 5:1. The filtrate was purified through a plug of silica, washed with hexane/acoet 5:1. The filtrate was concentrated affording pure alkenyl sulfides in the yields reported in Table 2. S16

Cyclopent-1-en-1-yl(decyl) sulfide 3p: 75% yield (72 mg). Brown oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.88 1.93 (m, 3H), 1.23 1.49 (m, 17H), 1.61 1.72 (m, 2H), 1.92 2.01 (m, 1H), 2.40 2.45 (m, 2H), 2.68 2.79 (m, 2H), 5.4 (m, 1H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 14.4 (CH 3 ), 22.9 (CH 2 ), 23.8 (CH 2 ), 29.5 (CH 2 ), 29.6 (CH 2 ), 29.7 (CH 2 ), 29.8 (CH 2 ), 29.8 (CH 2 ), 32.1 (2 x CH 2 ), 33.0 (CH 2 ), 36.4 (CH 2 ), 39.5 (CH 2 ), 122.3 (CH), 137.3 (C). EI-LRMS m/z 240 (M +, 42), 100 (100), 67 (48). HRMS (ESI-TOF) calc d for [C 15 H 28 S+H] +, 241.1984; found, 241.1989. Cyclopent-1-en-1-yl(phenyl) sulfide 3q: 13 55% yield (40 mg). Brown oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 1.93 2.03 (m, 2H), 2.40 2.45 (m, 4H), 5.75 (bs, 1H), 7.23 7.35 (m, 3H), 7.39 7.43 (m, 2H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 23.8 (CH 2 ), 33.0 (CH 2 ), 35.8 (CH 2 ), 127.0 (CH), 129.0 (2 x CH), 131.3 (2 x CH), 131.4 (CH), 134.3 (C). 135.8 (C). EI-LRMS m/z 176 (M +, 100), 67 (52). General procedure for the synthesis of alkenyl sulfides 3,4 from alkenyl tosylates. A solution of synthesize vinyl tosylate (α-tosyloxistyrene, 3 cyclohex-1-en-1-yl tosylate, 14 3,3- dimethylbut-1-en-2-yl tosylate, 15 hex-2-en-2-yl tosylate, 15 1-cyano-2-phenylvinyl tosylate 16 ) (1 equiv, 0.4 mmol), Pd 2 dba 3 (2.5 mol %, 0.01 mmol, 18.3 mg), CyPFtBu (5 mol %, 0.02 mmol, 11.1 mg) in dry toluene (0.8 ml) was stirred under a nitrogen atmosphere for 2 min. Then, thiophenol or 1-decanethiol (1.1 equiv, 0.44 mmol, 45 µl or 91 µl respectively) and LiHMDS (2.4 equiv, 0.96 mmol, 0.96 ml of a 1M solution in toluene) or Cs 2 CO 3 (2.0 equiv, 0.8 mmol, 282 mg) were added to the mixture and the resulting solution was stirred at 110 ºC for 24 h. After that, the reaction mixture was allowed to cool to room temperature and a solution of hexane/acoet 10:1 (10 ml) was added. The reaction mixture was filtered under vacuum through a plug of silica and washed with hexane/acoet 10:1. The filtrate was 13 Hopkins, P. B.; Fuchs, P. L.; J. Org. Chem., 1978, 43, 1208-1217. 14 Reeves, D. C.; Rodriguez, S.; Lee, H.; Haddad, N.; Krishnamurthy, D.; Senanayake, C. H.; Org. Lett., 2011, 13, 2495-2497. 15 Xie, L.; Zhen, X.; Huang, S.; Su, X.; Lin, M.; Li, Y. Green Chemistry, 2017, 19, 3530-3534. 16 Chen, N.; Lu, Y.; Gadamasetti, K.; Hurt, C. R.; Norman, M. H.; Fotsch, C.; J. Org. Chem., 2000, 65, 2603-2605. S17

purified through a plug of silica, washed with hexane/acoet 10:1. The filtrate was concentrated affording pure alkenyl sulfides in the yields reported in Scheme 3. 3,3-dimethylbut-1-en-2-yl phenyl sulfide 4n: 17 62% yield (48 mg). Yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 1.13 (s, 9H), 6.00 6.22 (m, 2H), 7.07 7.52 (m, 5H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 29.4 (3 x CH 3 ), 34.5 (C), 116.8 (CH 2 ), 126.0 (CH), 128.3 (2 x CH), 128.9 (2 x CH), 136.8 (C), 147.9 (C). EI-LRMS m/z 192 (M +, 40), 135 (100). Hex-2-en-2-yl phenyl sulfide 4o: 95% yield (73 mg). Mixture of diastereoisomers E/Z 1:1 (equivalent mixture to the starting alkenyl bromide). Yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.98 (t, J = 7.4 Hz, 6H), 1.45 1.53 (m, 4H), 1.93 (d, J = 0.8 Hz, 3H), 1.95 (d, J = 1.3 Hz, 3H), 2.16 (aq, J = 7.3 Hz, 2H), 2.35 (aq, J = 7.5 Hz, 2H), 5.88 (m, 1H), 5.94 (m, 1H), 7.20 7.26 (m, 2H), 7.28 7.39 (m, 8H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 13.8 (CH 3 ), 13.9 (CH 3 ), 18.1 (CH 3 ), 22.5 (CH 2 ), 22.7 (CH 2 ), 24.5 (CH 3 ), 31.4 (CH 2 ), 32.1 (CH 2 ), 126.1 (CH), 126.3 (CH), 128.7 (2 x CH), 128.8 (2 x CH), 128.9 (C), 129.1 (2 x CH), 130.0, (2 x CH) 130.1 (C), 135.1 (C), 135.6 (C), 135.9 (CH), 136.5 (CH). =. EI-LRMS m/z 192 (M +, 100), 163 (85), 135 (65), 130 (45). HRMS (ESI-TOF) calc d for [C 12 H 17 S+H] +, 193.1045; found, 193.1043. Cyclohex-1-en-1-yl(decyl) sulfide 4p: 84% yield (85 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.84 0.99 (m, 3H), 1.22 1.47 (m, 14H), 1.53 1.77 (m, 6H), 2.01 2.22 (m, 4H), 2.58 2.75 (m, 2H), 5.63 (td, J = 3.8, 1.9 Hz, 1H) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 14.1 (CH 3 ), 22.1 (CH 2 ), 22.7 (CH 2 ), 23.4 (CH 2 ), 26.3 (CH 2 ), 29.0 (CH 2 ), 29.1 (CH 2 ), 29.2 (CH 2 ), 29.3 (CH 2 ), 29.5 (CH 2 ), 29.6 (CH 2 ), 29.9 (CH 2 ), 30.8 (CH 2 ), 31.9 (CH 2 ), 122.9 (CH), 132.2 (C). EI-LRMS m/z 254 (M +, 65), 114 (100), 81 (55). HRMS (ESI-TOF) calc d for [C 16 H 30 S+H] +, 255.2141; found, 255.2139. 17 Trost, B. M.; Lavoie, A. C..; J. Am. Chem. Soc., 1983, 105, 5075-5090. S18

Cyclohex-1-en-1-yl(phenyl) sulfide 4q: 18 77% yield (59 mg). Pale yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 1.54 1.87 (m, 4H), 2.01 2.29 (m, 4H), 6.02 6.18 (m, 1H), 7.11 7.48 (m, 5H). ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 21.7 (CH 2 ), 23.6 (CH 2 ), 26.8 (CH 2 ), 30.0 (CH 2 ), 126.3 (CH), 128.8 (CH), 130.1 (CH), 131.4 (C), 132.8 (CH), 135.3 (C). EI-LRMS m/z 190 (M +, 100), 81 (70). 3-(Decylthio)-3-phenylacrylonitrile 4r: synthesized according to the general procedure by using Cs 2 CO 3 (2.0 equiv, 0.8 mmol, 261 mg) as base instead of LiHDMS. 63% yield (76 mg). Mixture of diastereoisomers E/Z 3:1 (equivalent mixture to the starting alkenyl tosylate). Yellow oil. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 0.82 0.99 (m, 6H, major + minor), 1.17 1.35 (m, 26H, maj + min), 1.45 1.56 (m, 2H, maj), 1.65 1.79 (m, 2H, min), 2.70 (dd, J = 7.4, 1.6 Hz, 2H, maj), 2.77 2.87 (m, 2H, min), 5.17 (s, 1H, min), 5.50 (s, 1H, maj), 7.43 7.59 (m, 10H, maj + min) ppm. 13 C NMR (75.4 MHz, CDCl 3 ) δ = 14.2 (2 x CH 3 ), 22.8 (CH 2 ), 27.8 (CH 2 ), 28.4 (CH 2 ), 28.7 (CH 2 ), 29.0 (CH 2 ), 29.1 (CH 2 ), 29.2 (CH 2 ), 29.4 (CH 2 ), 29.4 (CH 2 ), 29.5 (CH 2 ), 29.6 (CH 2 ), 29.7 (CH 2 ), 29.7 (CH 2 ), 29.9 (CH 2 ), 32.0 (CH 2 ), 32.0 (CH 2 ), 33.4 (CH 2 ), 39.4 (CH 2 ), 96.1 (CH), 116.9 (C), 128.1 (2 x CH), 128.3 (2 x CH, min)128.8 (2 x CH, min), 129.0 (2 x CH), 130.7 (CH), 136.9 (C), 163.5 (2 x C). EI-LRMS m/z 301 (M +, 30), 261 (40), 161 (100), 121 (65). HRMS (ESI-TOF) calc d for [C 19 H 28 NS+H] +, 302.1937; found, 302.1934. Synthesis of (4-(2-bromovinyl)phenyl)(phenyl)methanone 1g Under N 2 atmosphere, a solution of 4-bromonbenzophenone (1.30 g, 5 mmol, 1.0 equiv.) and acrylic acid (0.5 g, 7 mmol, 1.4 equiv.) in dry dimethylacetamide (DMA) (15 ml) was prepared. Then Pd(OAc) 2 (11 mg, 0.05 mmol, 1 mol%), P(o-tolyl) 3 (30 mg, 0.1 mmol, 2 mol%) and triethylamine (2.1 ml, 15 18 Kennedy, N.; Lu, G.; Liu, P.; Cohen, T.; J. Org. Chem., 2015, 80, 8571-8572 S19

mmol, 3 equiv.) were added. The mixture was heated to 130 ºC in an oil bath a the reaction was monitored by GC-MS. After 4 h the reaction was quenched by addition of NaHCO 3 (20 ml, saturated solution). The water phase was washed with Et 2 O (2 x 15 ml). Then the water phase was acidified to ph = 1 after addition of HCl (6 M), and extracted with EtOAc (3 x 30 ml). The combined organic phase was concentrated affording the (E)-3-(4-benzoylphenyl)acrylic acid pure enough to the next step. In a round bottom flask PIDA (diacetoxyiodobenzene) (1.42 g, 4.4 mmol, 1.1 equiv.) and tetraethylammonium bromide (1.0 g, 4.8 mmol, 1.2 mmol) were suspended in CH 2 Cl 2 under nitrogen atmosphere at 0 ºC. After 5 min, (E)-3-(4-benzoylphenyl)acrylic acid (1.0 g, 4 mmol, 1 equiv.) was added. The reaction was monitore until total depletion of the starting materials. The reaction mixture was diluted with CH 2 Cl 2, washed with 10 % aq. sodium bisulfite solution (2 x 30 ml), 10 % NaHCO 3 (2 x 30 ml), water (20 ml) and brine (20 ml). The organic layer was dried over Na 2 SO 4 and concentrated. The crude product was purified by flash chromatography on silica gel (Hexane:AcOEt = 10:1) affording 0.8 g (70%) of (4-(2-bromovinyl)phenyl)(phenyl)methanone (colorless oil) as a mixture Z/E 9:1. 1 H NMR (300 MHz, CDCl 3, 25 ºC) δ = 6.59 (d, J = 8.2 Hz, 1H), 6.95 (d, J = 14.1 Hz, 1H), 7.13 7.21 (m, 1H), 7.35 7.45 (m, 10H), 7.46 7.54 (m, 3H), 7.54 7.66 (m, 2H), 7.71 7.89 (m, 4H). 13 C NMR (75.4 MHz, CDCl 3 ) δ = 108.6 (CH min) 108.7 (CH), 125.9 (CH), 128.3 (2 x CH), 128.8 (2 x CH), 129.9 (C), 130.0 (2 x CH), 130.0 (2 x CH), 130.7 (CH, min), 131.6 (CH), 132.5 (CH), 136.3 (C, min), 137.0 (C, min), 137.5 (C), 138.9 (C), 196.1 (C). EI-LRMS m/z 288(M +, 98), 286(100). HRMS (ESI-TOF) calc d for [C 15 H 11 BrO+H] +, 287.0066; found, 287.0067. S20

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