Binuclear Fe-Complexes as Catalyst for the Ligand-free Regioselective Allylic Sulfenylation.

Transcription

1 Binuclear Fe-Complexes as Catalyst for the Ligand-free Regioselective Allylic Sulfenylation. Michael S. Holzwarth, Wolfgang Frey, Bernd Plietker* Institut für Organische Chemie, Fakultät Chemie, Universität Stuttgart, Pfaffenwaldring 55, D Stuttgart, Germany. General Remarks S-2 I. Preparation of iron complexes S-2 II. Preparation of starting materials S-5 III. Iron catalyzed allylic sulfenylation S-8 IV. References S-34 V. Spectra S-35 VI. X-Ray S-60 VII. Chromatograms S-76 S1

2 General remarks All the reactions and manipulations which are sensitive to air or moisture were performed under dry nitrogen by using standard Schlenk techniques. All solvents were purified prior to use. Thiols were purchased from Acros Organics, Sigma Aldrich or Alfa Aesar. NMR spectra were recorded on a Bruker AV 300 spectrometer at 300 MHz ( 1 H-NMR), 75 MHz ( 13 C-NMR), a Bruker AV 500 spectrometer at 500 MHz ( 1 H- NMR), MHz ( 13 C-NMR) or a Bruker AV 250 spectrometer at 250 MHz ( 1 H- NMR), 62.5 MHz ( 13 C-NMR). Chemical shifts were reported in ppm down field using tetramethylsilane as an internal standard. IR spectra were measured on a Bruker Vector 22 FT-IR spectrometer in an ATR mode. Mass spectra were measured using electrospray ionization on a Bruker Micro-TOF-Q. I. Preparation of iron complexes tetra-n-butylammonium tris-carbonylnitrosoferrate [TBAFe]/4 1. Sodium nitrite (8.4 g, 120 mmol) and tetra-butylammonium bromide (38.0 g, 120 mmol) were dissolved in degassed water (40 ml) under a nitrogen atmosphere at room temperature. A solution of iron pentacarbonyle (23.6 g, 120 mmol) in degassed dichloromethane (40 ml) was added to the solution at room temperature. The reaction mixture was stirred at room temperature for 3 h. The organic phase was separated, extracted with distilled water (2 x 20 ml), dried over Na 2 SO 4, filtered and concentrated in vacuum. The resulting dark brown oily residue was diluted in a minimum amount of methanol and added dropwise to degassed water (500 ml) with vigorous stirring. After stirring for 30 min a yellow solid precipitated and was isolated as by filtration. The solid was again taken up in a small amount of methanol and filtered through a silica pad using a mixture of dichloromethane/methanol (3:1) as the eluent. After removal of the solvent TBAFe was obtained as a yellowish brown solid (111 mmol, 92 %). 1 H-NMR (300 MHz, CD 2 Cl 2 ) δ 3.18 (s, 8H), 1.65 (s, 8H), 1.46 (s, 8H), 1.03 (s, 12H) ppm; 13 C-NMR (125 MHz, CD 2 Cl 2 ) δ 225.1, 59.3, 24.3, 20.1, 13.8 S2

3 ppm; IR (Film) ν 2963 (w), 2876 (w), 1975 (m), 1851 (s), 1635 (s), 1470 (m), 1379 (w), 1035 (w), 883 (w), 737 (w), 621 (s), 524 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 170 (100), 142 (10), 114 (6), 88 (3); HRMS (ESI-HR) calc d C 3 FeNO 4 : , found: Dibenzylthiolato dinitrosyl iron dimer 6 2 Iron(II)sulfate (5.0 g, 180 mmol) was dissolved in 4 M aqueous sulfuric acid solution (50 ml). Then sodium nitrite (2.0 g, 230 mmol) and benzyl mercaptan (5.0 ml, 420 mmol) were added simultaneously at room temperature. The resulting brown solution was stirred at room temperature for further 10 minutes. Then the ph value of the reaction mixture was set to 6 with a 6 M aqueous sodium hydroxide solution. The green precipitate was filtered and washed with water (25 ml), iso-propanol (10 ml) and petroleum ether (5 ml). After drying the black solid in vacuo it was extracted with benzene (3 x 50 ml) and evaporated to dryness. The crude product was purified by recrystallization from acetone/water. Iron complex 6 was obtained as a brown powder (2.7 g, 32 %). 1 H-NMR (300 MHz, CD 2 Cl 2 ) δ (m, 10H), 4.44 (s, 2H), 4.39 (s, 2H) ppm; 13 C-NMR (63 MHz, CD 2 Cl 2 ) δ 129.9, 129.8, 129.7, 129.6, 128.8, 49.7, 48.8 ppm; IR (Film) ν 1769 (s), 1720 (s), 1492 (m), 1452 (m), 1227 (w), 1068 (w), 1027 (w), 912 (w), 759 (m), 695 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 478 (5), 448 (100), 418 (63), 388 (36), 358 (55), 324 (4), 297 (6), 267 (55), 221 (1), 176 (12), 144 (5), 121 (1), 91 (80), 65 (6), 30 (2); HRMS (ESI-HR) calc d C 14 H 14 Fe 2 N 4 O 4 S 2 : , found: ; R f 0.41 (petroleum ether). tetra-n-butylammonium bis-iodoso bis-nitroso ferrate 3 TBAFe 4 (824 mg, 2 mmol) was dissolved in methylene chloride (25 ml) and iodine (900 mg, 3.5 mmol) was added slowly at 0 C. After stirring for 2 h at room temperature the solution was evaporated to dryness and filtered through celite (eluent: methylene chloride). The solvent was removed in vacuum and the desired crude product was obtained as a S3

4 black solid. The formation of tetra-n-butylammonium bis-iodoso bis-nitroso ferrate was confirmed by IR and found sufficently pure for further conversion. IR (Film) ν 2958 (m), 2931 (m), 2872 (m), 1769 (s), 1711 (s), 1468 (s), 1379 (w), 1168 (w), 1031 (w), 879 (m), 735 (m) cm -1 ; GC/MS (ESI, 70 ev) m/z (%) = 370 (1), 255 (1), 127 (100). tetra-n-butylammonium bis-thiophenolato bis-nitroso ferrate 5 4 Crude tetra-nbutylammonium bis-iodoso bis-nitroso ferrate (2.5 mmol) was dissolved in THF/MeOH (2:1, 30 ml) and sodium thiophenolate (1.3 g 10 mmol) was added. The reaction mixture was allowed to stir overnight at room temperature. After removal of the solvent the residue was taken up in methylene chloride and filtered through a plug of basic aluminium oxide. After addition of n-pentane product 5 was obtained at -18 C as black crystals (28 %, 234 mg). 1 H-NMR (300 MHz, CD 2 Cl 2 ) δ (m, 10 H), 3.12 (s, 8H), 1.59 (s, 8H), 1.39 (s, 8H), 0.96 (s, 12H) ppm; IR (Film) ν 2957 (m), 2872 (m), 1733 (s), 1686 (s), 157(m), 1471 (s), 1378 (m), 1166 (w), 1084 (w), 1067 (w), 1025 (w), 880 (m), 737 (s), 690 (s) cm -1 ; GC/MS (ESI, 70 ev) m/z (%) = 334 (3), 304 (100), 274 (1), 225 (2), 157 (2), 109 (1); HRMS (ESI-HR) calc d C 12 H 10 FeN 2 O 2 S 2 : , found: [(SIPr)Fe(SBn)(NO) 2 ] 8. Ligand 2 (854 mg, 2 mmol) and sodium tert-butylat (192 mg, 2 mmol) were dissolved in THF (40 ml). The resulting solution was stirred at room temperature for 1 h. Then iron complex 6 (478 mg, 1 mmol) was added and the reaction mixture was stirred for 1 h at room temperature. The resulting deep red solution was filtered through celite and the solvent was removed in vacuo. The crude product was purified by column chromatography on neutral alumina oxide (npentane/methylene chloride 1/0 -> 0/1) and product 8 was obtained as a red-brown solid (200 mg, 32 %). Crystals which were suitable for x-ray analysis were obtained by slow evaporation from acetonitrile at -20 C. IR (Film) ν 2963 (m), 1756 (s), 1700 S4

5 (s), 1475 (m), 1452 (m), 1430 (m), 1284 (m), 1266 (m), 1242 (m), 804 (m), 758 (m), 732 (s), 700 (s) cm -1 ; GC/MS (ESI, 70 ev) m/z (%) = 506 (11), 391 (100); HRMS (ESI-HR) calc d C 27 H 38 FeN 4 O 2 : , found: II. Preparation of starting materials 4-Acetamidothiophenol 5 Experimental procedure: p-mercapto aniline (1.3g, 10 mmol) was dissolved in ethyl acetate (50 ml) and cooled to 0 C. Acetic anhydride (1.0 ml, 11 mmol) was added carefully and the reaction mixture was allowed to warm to room temperature within 1 h. The reaction mixture was diluted with ethyl acetate (50 ml) then washed with aqueous hydrochloric acid (1 N, 50 ml) and brine (50 ml). After drying over sodium sulfate the product was purified by flash chromatography on silica (petroleum ether/ethyl acetate 1:1). Off-white solid, mp: 143 C, isolated yield: 78 % (1.01 g); 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 4H), 3.42 (s, 1H), 2.17 (s, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 168.2, 136.1, 130.7, 125.3, 120.6, 24.6 ppm; IR (Film) ν 3292 (w), 3179 (w), 3108 (w), 1658 (s), 1591 (s), 1521 (s), 1489 (s), 1392 (s), 1365 (s), 1314 (s), 1257 (m), 1100 (m), 1011 (m), 818 (s), 741 (m), 708 (m), 603 (m), 582 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 167 (56), 125 (100), 109 (7), 97 (22), 93 (24), 81 (21), 69 (18), 55 (15); R f 0.40 (petroleum ether/ethyl acetate 1:2). Cystin methylester hydrochloride 6 S5

6 Experimental procedure: Methanol (20 ml) was cooled to 0 C and thionyl chloride (3.2 ml, 44 mmol) was added dropwise. Then L-cystine (2.4 g, 20 mmol) was added at room temperature and the reaction mixture was heated to reflux overnight. After removal of the solvent the residue was suspended in diethyl ether and cooled to 0 C. The crude product was filtered off and recrystallized from hot methanol by addition of diethyl ether. The colourless crystals were filtered off and washed with a solution of diethyl ether/methanol (5:1) twice. After drying in vacuo the product was obtained as white crystals (12.3 g, 73%). [α] 20 D (c = 0.5, MeOH); 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), 3.87 (s, 6H), (m, 4H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 172.1, 56.9, 54.4, 38.5 ppm; IR (Film) ν 2807 (b), 1742 (s), 1564 (w), 1539 (w), 1496 (m), 1430 (m), 1401 (w), 1381 (w), 1326 (w), 1242 (s), 1196 (s), 1060 (m), 991 (m), 926 (m), 881 (m), 842 (m), 821 (m), 774 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 323 (4), 301 (3), 291 (13), 269 (100), 242 (8), 166 (51), 134 (29), 101 (3), 88 (5); HRMS (ESI-HR) calc d for C 8 H 16 N 2 O 4 S 2 : , found: N-(Benzoyl)-L-cystine methyl ester 7 Experimental procedure: Cystin methylester hydrochloride (1.7 g, 5 mmol) was suspended in THF (30 ml) and cooled to 0 C. Pyridine (7.2 ml, 50 mmol) and benzoyl chloride (1.4 ml, 12 mmol) were added and the reaction mixture was stirred overnight at room temperature. After addition of water (40 ml) the reaction mixture was extracted with ethyl acetate (3 x 25 ml). The combined organic layers were washed with 2 N aqueous hydrochloric acid (2 x 25 ml), saturated sodium hydrogencarbonate solution (1 x 25 ml) and brine (1 x 25 ml). The organic phase was dried over sodium sulfate, filtered and evaporated to dryness to obtain the yellow S6

7 crude product which was recrystallized from methylene chloride/diethyl ether to yield the pure product in 55 % (1.3 g) as a white solid. [α] 20 D (c = 0.8, EtOH); mp: 181 C; 1 H-NMR (250 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 7.12 (d, J = 7.3 Hz, 1H), (m, 1H), 3.78 (s, 3H), 3.35 (d, J = 5.1 Hz, 2H) ppm; 13 C-NMR (50 MHz, CDCl 3 ) δ 170.9, 167.1, 133.5, 132.0, 128.6, 127.2, 52.9, 52.3, 40.9 ppm; IR (Film) ν 3306 (w), 1735 (s), 1635 (s), 1602 (w), 1579 (w), 1522 (s), 1488 (m), 1434 (w), 1293 (m), 1267 (m), 1213 (s), 1160 (s), 1097 (w), 1024 (w), 1001 (w), 837 (w), 715 (m), 691 (s), 674 (m) cm -1 ; GC/MS (ESI, 70 ev) m/z (%) = 477 (15), 445 (6), 417 (2), 272 (2), 238 (100), 222 (1), 135 (3), 105 (2); R f 0.37 (petroleum ether/ethyl acetate 1:1). N-(Benzoyl)-L-cysteine methyl ester 8 Experimental procedure: N-(Benzoyl)-L-cysteine methyl ester was prepared according to an experimental procedure of Corey and coworkers 5. N-(Benzoyl)-Lcystine methyl ester (1.2 g, 2.5 mmol) was placed in a flask and dimethoxyethan (35 ml), methanol (10 ml), water (5 ml) and triphenyl phoshine (2.0 g, 7.5 mmol) were added. The reaction mixture was heated to 90 C overnight. After cooling down to room temperature methylene chloride was added and the aqueous layer was extracted with methylene chloride (3 x 50 ml). The combined organic layers were dried over sodium sulfate. After filtration and removal of the solvents the crude product was subjected to column chromatography on silica gel (petroleum ether/ethyl acetate 3:1) to obtain the product as a white solid (686 mg, 57 %). [α] 20 D (c = 1, EtOH); mp: 62 C; 1 H-NMR (250 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 7.07 (s, 1H), (m, 1H), 3.84 (s, 3H), 3.15 (ddd, J = 9.0, 4.0, 1.3 Hz, 2H), 1.41 (t, J = 9.0 Hz, 1H) ppm; 13 C-NMR (50 MHz, CDCl 3 ) δ 170.7, 133.6, 132.0, 128.7, 127.2, 53.9, 53.0, 27.0 ppm; IR (Film) ν 3274 (w), 2950 (w), 1732 (s), 1641 (s), 1529 (s), 1488 (m), 1434 (m), 1322 (s), 1293 (m), 1253 (m), S7

8 1218 (s), 1192 (m), 1174 (m), 1097 (m), 1065 (m), 999 (m), 911 (w), 801 (w), 695 (s), 637 (m), 616 (w) cm -1 ; GC/MS (ESI, 70 ev) m/z (%) = 240 (14), 222 (8), 208 (10), 180 (13), 105 (100); R f 0.61 (petroleum ether/ethyl acetate 1:1). III. Iron-catalyzed allylic sulfenylation General Procedure for [Bu 4 N] 2 [((BnS)(NO) 2 Fe) 2 ]-catalyzed Allylic Sulfenylation (GP-I): Iron complex 6 (4.8 mg, 0.01 mmol) was dissolved in THF (0.5 ml) and potassium hydride (1 mg, 0.02 mmol) was added. After the reaction mixture was stirred for 3 h at room temperature a deep green solution of iron complex 7 was obtained. Then Bu 4 NBr (6.4 mg, 0.02 mmol), carbonate (4 mmol) and benzyl mercaptan (4 mmol) were added successively. The Schlenk tube was closed and heated to 40 C for 18 h. After evaporation of the solvent the product was isolated by column chromatography on silica. The product was obtained as a mixture of regioisomers, which were separated by column chromatography on silica. a) Allylic Substitution with thiophenol The product was obtained according to GP-I as a mixture of regioisomeres 9-A/9-B 94:6. The product was isolated by column chromatography on silica (petroleum ether) in 93 % (165 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether). Major isomer: (1,1-Dimethyl-allylsulfanyl)-benzene 9-A 9 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 5.96 (dd, J = 17.3, 10.6 Hz, 1H), 4.91 (dd, J = 10.1, 0.5 Hz, 1H), 4.72 (dd, J = 16.9, 0.4 Hz, 1H), 1.36 (s, 6H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 144.7, 137.2, 132.4, S8

9 128.7, 128.3, 111.6, 50.0, 27.5 ppm; IR (Film) ν 2964 (m), 2923 (m), 2360 (m), 2341 (w), 1634 (w), 1473 (m), 1438 (m), 1377 (w), 1361 (w), 1121 (s), 1025 (w), 933 (w), 911 (m), 749 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 178 (18), 135 (1), 110 (100), 91 (1), 84 (2), 77 (5), 69 (84), 51 (9); R f 0.30 (petroleum ether). Minor isomer: 3-Methyl-but-2-enyl sulfanyl-benzene 9-B 10 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), (m, 1H), 3.54 (d, J = 7.7 Hz, 2H), 1.71 (s, 3H), 1.59 (s, 3H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 136.9, 136.4, 129.7, 128.7, 126.0, 119.3, 32.2, 25.7, 17.7 ppm; IR (Film) ν 3059 (w), 2976 (w), 2929 (w), 1581 (m), 1478 (m), 1439 (m), 1376 (w), 1088 (w), 1024 (m), 737 (s), 689 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 178 (43), 161 (1), 147 (1), 135 (3), 110 (100), 99 (1), 91 (2), 77 (6), 69 (83), 65 (26), 51 (11); R f 0.30 (petroleum ether). b) Allylic Substitution with benzyl mercaptan The product was obtained according to GP-I as a mixture of regio isomeres 3-A/3-B 93:7. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 80:1) in 84 % (161 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether). Major isomer: (1,1-Dimethyl-allylsulfanylmethyl)-benzene 3-A 11 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), 5.92 (dd, J = 17.3, 10.6 Hz, 1H), (m, 2H), 3.60 (s, 2H), 1.39 (s, 6H) ppm; 13 C-NMR (63 MHz, CDCl 3 ) δ 144.6, 138.4, 129.0, 128.4, 126.8, 111.6, 47.3, 34.1, 27.4 ppm; IR (Film) ν 3029 (w), 2964 (w), 1633 (w), 1494 (m), 1454 (m), 1362 (m), 1124 (s), 1029 (w), 995 (m), 912 (s), 764 (w), 695 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 192 (66) [M + ], S9

10 177 (2), 124 (35), 101 (19), 91 (83), 77 (6), 69 (100), 65 (10), 45 (10), 41 (35); R f 0.66 (petroleum ether/ethylacetate 20:1). c) Allylic Substitution with 2-methyl-thiophenol The product was obtained according to GP-I as a mixture of regio isomeres 12-A/12- B 87:13. The product was isolated by column chromatography on silica (petroleum ether) in 78 % (150 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether). Major isomer: 1-Methyl-2-(1,1-dimethyl-allylsulfanyl)-benzene 12-A colouless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 1H), (m, 2H), (m, 1H), 5.98 (dd, J = 17.0, 10.5 Hz, 1H), 4.89 (dd, J = 10.4, 1.1 Hz, 1H), 4.73 (dd, J = 17.2, 0.8 Hz, 1H), 2.48 (s, 3H), 1.37 (s, 6H) ppm; 13 C-NMR (63 MHz, CDCl 3 ) δ 144.9, 143.5, 138.5, 131.9, 130.3, 128.8, 125.6, 111.4, 51.0, 27.5, 26.9, 21.8 ppm; IR (Film) ν 2973 (w), 2927 (w), 1588 (w), 1466 (m), 1455 (m), 1378 (m), 1063 (m), 1043 (m), 742 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 192 (55), 166 (1), 149 (2), 137 (2), 124 (100), 108 (1), 91 (24), 77 (10), 69 (95), 65 (5), 53 (5), 41 (43); HRMS (ESI-HR) calc d for C 12 H 16 S: , found: ; R f 0.62 (petroleum ether). Minor isomer: 1-Methyl-2-(3-methyl-but-2-enylsulfanyl)-benzene 12-B Colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 1H), (m, 3H), (m, 1H), 3.51 (d, J = 7.9 Hz, 2H), 2.37 (s, 3H), 1.72 (s, 3H), 1.61 (s, 3H) ppm; 13 C-NMR (63 MHz, CDCl 3 ) δ 145.9, 137.6, 136.7, 129.9, 128.4, 126.2, 125.6, 118.9, 31.4, 25.7, 20.4, 17.7 ppm; IR (Film) ν 2974 (w), 2920 (w), 1588 (w), 1466 S10

11 (m), 1455 (m), 1378 (w), 1063 (w), 1042 (m), 742 (s), 709 (w) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 246 (32), 192 (53), 180 (1), 149 (2), 124 (100), 84 (46), 77 (10), 69 (86), 49 (50), 41 (33); HRMS (ESI-HR) calc d for C 12 H 16 S: , found: ; R f 0.60 (petroleum ether). d) Allylic Substitution with 3-methyl-thiophenol The product was obtained according to GP-I as a mixture of regio isomeres 11-A/11- B 93:7. The product was isolated by column chromatography on silica (petroleum ether) in 93 % (178 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether). Major isomer: 2-Methyl-2-(1,1-dimethyl-allylsulfanyl)-benzene 11-A colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 1H), (m, 1H), (m, 1H), 6.10 (dd, J = 17.4, 10.6 Hz, 1H), 4.92 (dd, J = 10.4, 0.8 Hz, 1H), 4.77 (dd, J = 17.1, 1.0 Hz, 1H), 2.15 (s, 3H), 1.41 (s, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 145.4, 138.3, 138.1, 134.7, 133.1, 129.7, 127.9, 111.4, 49.8, 27.7, 21.0 ppm; IR (Film) ν 2966 (w), 1591 (m), 1474 (s), 1440 (m), 1376 (s),1327 (w), 1120 (s), 1045 (s), 994 (s), 910 (s), 856 (m), 779 (s), 693 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 192 (38), 149 (1), 140 (4), 124 (100), 108 (2), 91 (16), 77 (4), 69 (60), 41 (25); HRMS (ESI-HR) calc d for C 12 H 16 S: , found: ; R f 0.65 (petroleum ether). Minor isomer: 2-Methyl-2-(3-methyl-but-2-enylsulfanyl)-benzene 11-B S11

12 Colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 3H), (m, 1H), (m, 1H), 3.53 (d, J = 7.7 Hz, 2H), 2.32 (s, 3H), 1.71 (s, 3H), 1.60 (s, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 138.5, 136.6, 136.3, 130.2, 128.6, 126.8, 126.5, 119.4, 32.2, 25.7, 21.3, 17.7 ppm; IR (Film) ν 2973 (w), 2917 (w), 1715 (w), 1592 (m), 1573 (w), 1474 (m), 1447 (m), 1376 (m), 1216 (w), 1101 (w), 1081 (w), 855 (m), 770 (s), 687 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 192 (67), 149 (2), 124 (100), 108 (2), 91 (16), 77 (5), 69 (64), 41 (27); HRMS (EI) calc d for C 12 H 16 S: , found: ; R f 0.63 (petroleum ether). e) Allylic Substitution with 4-methyl-thiophenol The product was obtained according to GP-I as a mixture of regio isomeres 10- A/10-B 94:6. The product was isolated by column chromatography on silica (petroleum ether) in 76 % (146 mg) combined yield. Major isomer: 3-Methyl-2-(1,1-dimethyl-allylsulfanyl)-benzene 10-A colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 5.95 (dd, J = 17.4, 10.6 Hz, 1H), 4.90 (dd, J = 10.4, 0.9 Hz, 1H), 4.72 (dd, J = 17.2, 0.9 Hz, 1H), 2.34 (s, 3H), 1.34 (s, 6H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 144.8, 138.8, 137.2, 129.1, 128.9, 111.5, 49.8, 27.4, 21.2 ppm; IR (Film) ν 2974 (w), 2920 (w), 1491 (m), 1448 (m), 1377 (m), 1089 (m), 1040 (m), 1015 (m), 804 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 192 (14), 124 (100), 108 (2), 91 (37), 77 (12), 69 (51), 53 (9); HRMS (EI) calc d for C 12 H 16 S: , found: ; R f 0.61 (petroleum ether). Allylic Substitution with 3,5-dimethyl-thiophenol The product was obtained according to GP-I as a mixture of regio isomeres 20-A/20- B 94:6. The product was isolated by column chromatography on silica (petroleum ether) in 72 % (149 mg) combined yield. Major isomer: 2,4-Dimethyl-2-(1,1-dimethyl-allylsulfanyl)-benzene 20-A S12

13 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 1H), 5.96 (dd, J = 17.1, 10.8 Hz, 1H), 4.92 (dd, J = 10.4, 0.8 Hz, 1H), 4.76 (dd, J = 17.4, 0.8 Hz, 1H), 2.29 (s, 6H), 1.35 (s, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 144.9, 137.8, 134.7, 130.4, 127.0, 111.3, 49.7, 27.6, 21.1 ppm; IR (Film) ν 2964 (w), 2918 (w), 1599 (m), 1580 (m), 1454 (m), 1376 (w), 1360 (w), 1121 (s), 993 (m), 909 (s), 849 (s), 690 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 206 (20), 189 (1), 163 (2), 138 (100), 121 (4), 105 (33), 91 (12), 77 (12), 69 (50), 53 (11); HRMS (ESI-HR) calc d for C 13 H 18 S: , found: ; R f 0.44 (petroleum ether). f) Allylic Substitution with 4-methoxy-thiophenol The product was obtained according to GP-I as a mixture of regio isomeres 13-A/13- B 93:7. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 40:1) in 97 % (202 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether/ethyl acetate 20 : 1). Major isomer: 1-(1,1-Dimethyl-allylsulfanyl)-4methoxy-benzene 13-A colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 5.94 (dd, J = 17.3, 10.5 Hz, 1H), 4.90 (dd, J = 10.4, 1.1 Hz, 1H), 4.70 (dd, J = 16.9, 0.5 Hz, 1H), 3.81 (s, 3H), 1.33 (s, 6) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 160.3, 144.7, 138.8, 123.3, 113.9, 111.5, 55.3, 49.7, 27.3 ppm; IR (Film) ν 2928 (w), 1591 (m), 1571 (w), 1491 (s), 1461 (m), 1440 (m), 1376 (w), 1284 (m), 1241 (s), 1171 (m), 1103 (m), 1030 (s), 823 (s), 798 (m), 638 (m), 625 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 208 (37), 140 (100), 125 (15), 96 (4), 69 (26), 41 (16); HRMS (ESI-HR) calc d for C 12 H 16 OS: , found: ; R f 0.72 (petroleum ether/ethyl acetate 10:1). Minor isomer: 1-Methoxy-4-(3-methyl-but-2-enylsulfanyl)-benzene 13-B 12 S13

14 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), (m, 1H), 3.80 (s, 3H), 3.42 (d, J = 7.8 Hz, 2H), 1.69 (s, 3H), 1.46 (s, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 159.0, 135.9, 134.0, 126.6, 119.8, 114.3, 55.3, 34.3, 25.7, 17.5 ppm; IR (Film) ν 2911 (w), 1591 (m), 1492 (s), 1461 (m), 1440 (m), 1284 (m), 1241 (s), 1172 (s), 1103 (m), 1031 (m), 824 (m), 798 (w), 638 (w), 626 (w) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 208 (32), 140 (100), 125 (19), 108 (2), 96 (16), 69 (33), 53 (5), 41 (31); R f 0.58 (petroleum ether/ethyl acetate 10:1). g) Allylic Substitution with 3,4-dimethoxy-thiophenol The product was obtained according to GP-I as a mixture of regio isomeres 14-A/14- B 94:6. The product was isolated by column chromatography on silica (petroleum ether) in 83 % (199 mg) combined yield. Major isomer: 1-(1,1-Dimethyl-allylsulfanyl)-3,4 dimethoxy-benzene 14-A yellow oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 1H), 5.97 (dd, J = 17.4, 10.6 Hz, 1H), 4.92 (dd, J = 10.6, 0.9 Hz, 1H), 4.74 (dd, J = 17.3, 0.9 Hz, 1H), 3.87 (d, J = 4.7 Hz, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 148.8, 147.2, 143.9, 129.2, 122.6, 119.1, 110.5, 109.7, 54.9, 54.8, 48.9, 28.7, 26.3 ppm; IR (Film) ν 2918 (w), 1742 (w), 1461 (m), 1371 (s), 1314 (m), 1229 (m), 1186 (m), 1140 (m), 1057 (w), 971 (w), 913 (w), 746 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 238 (41) [M], 170 (100), 155 (24), 127 (2), 109 (2), 96 (2), 69 (17), 41 (11); HRMS (ESI-HR) calc d for C 13 H 18 O 2 S: , found: 261,0911; R f 0.24 (petroleum ether/ethyl acetate 20:1). S14

15 h) Allylic Substitution with 4-fluor-thiophenol The product was obtained according to GP-I as a mixture of regio isomeres 18-A/18- B 88:12. The product was isolated by column chromatography on silica (petroleum ether) in 50 % (98 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether). Major isomer: 2-Fluor-(1,1-dimethyl-allylsulfanyl)-benzene 18-A colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 5.93 (dd, J = 17.4, 10.5 Hz, 1H), 4.91 (dd, J = 10.4, 1.0 Hz, 1H), 4.68 (dd, J = 17.7, 0.3 Hz, 1H), 1.34 (s, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ (d, J C-F = Hz), 144.4, (d, J C-F = 9.0 Hz), 127.8, (d, J C-F = 21.6 Hz), 111.8, 50.0, 27.2 ppm; IR (Film) ν 2966 (w), 1589 (m), 1488 (s), 1362 (w), 1220 (s), 1155 (m), 1121 (m), 1088 (w), 994 (w), 912 (m), 830 (s), 816 (m), 685 (m), 637 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 196 (41), 169 (1), 153 (1), 128 (75), 108 (4), 83 (16), 69 (100), 53 (3), 41 (43); HRMS (ESI-HR) calc d for C 11 H 13 FS: , found: ; R f 0.44 (petroleum ether). Minor isomer: 3-Fluor-(3-methyl-but-2-enylsulfanyl)-benzene 18-B colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), (m, 1H), 3.47 (d, J = 7.8 Hz, 2H), 1.70 (s, 3H), 1.50 (s, 3H) ppm; 13 C- NMR (63 MHz, CDCl 3 ) δ 136.4, 133.3, 133.2, 119.4, 115.9, 115.6, 33.6, 25.6, 17.6 ppm; IR (Film) ν 2974 (w), 2916 (w), 1588 (m), 1489 (s), 1220 (s), 1153 (m), 1083 (m), 1042 (s), 1011 (m), 831 (s), 814 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 196 (49), S15

16 153 (1), 128 (60), 108 (3), 83 (24), 69 (100), 53 (6), 41 (51); HRMS (ESI-HR) calc d for C 11 H 13 FS: , found: ; R f 0.45 (petroleum ether). i) Allylic Substitution with 4-chlor-thiophenol The product was obtained according to GP-I as a mixture of regio isomeres 17-A/17- B 87:13. The product was isolated by column chromatography on silica (petroleum ether) in 68 % (145 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether). Major isomer: 3-Chlor-(1,1-dimethyl-allylsulfanyl)-benzene 17-A 13 yellow oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 5.93 (dd, J = 17.1, 10.8 Hz, 1H), 4.92 (dd, J = 10.1, 0.4 Hz, 1H), 4.71 (dd, J = 16.9, 0.4 Hz, 1H), 1.35 (s, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 144.4, 138.3, 135.1, 131.0, 130.8, 129.2, 128.5, 111.9, 50.3, 27.3 ppm; IR (Film) ν 2972 (w), 2913 (w), 1474 (s), 1447 (m), 1386 (m), 1218 (w), 1093 (s), 1010(s), 809 (s), 744(m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 212 (40), 188 (1), 144 (51), 108 (14), 69 (100), 53 (3), 41 (35); HRMS (ESI-HR) calc d for C 11 H 13 ClS: , found: ; R f 0.43 (petroleum ether). Minor isomer: 3-Chlor-(3-methyl-but-2-enylsulfanyl)-benzene 17-B 13 yellow oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 4H), (m, 1H), 3.44 (d, J = 7.7 Hz, 2H), 1.63 (s, 3H), 1.51 (s, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ , 134.4, 131.1, 130.2, 127.8, 118.0, 31.5, 24.6, 16.7 ppm; IR (Film) ν 2968 (w), 2917 (w), 2360 (m), 2341 (m), 1315 (m), 1260 (m), 1151 (s), 1087 (s), 1014 (s), 798 S16

17 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 212 (14), 157 (6), 144 (47), 108 (31), 99 (7), 69 (100), 53 (7); R f 0.41 (petroleum ether). j) Allylic Substitution with 4-brom-thiophenol The product was obtained according to GP-I as a mixture of regio isomeres 16-A/16- B 84:16. The product was isolated by column chromatography on silica (petroleum ether) in 81 % (207 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether). Major isomer: 3-Brom-2-(1,1-dimethyl-allylsulfanyl)-benzene 16-A colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 5.93 (dd, J = 17.4, 10.6 Hz, 1H), 4.93 (dd, J = 10.2, 0.4 Hz, 1H), 4.71 (dd, J = 17.0, 0.4 Hz, 1H), 1.35 (s, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 144.4, 138.6, 131.7, 131.3, 123.4, 112.0, 50.3, 27.4 ppm; IR (Film) ν 2970 (w), 2913 (w), 1472 (s), 1448 (m), 1384 (m), 1218 (w), 1090 (s), 1068 (m), 1006 (s), 804 (s), 729 (w) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 258 (25), 190 (33), 161 (1), 147 (1), 108 (16), 82 (2), 69 (100), 41 (27); HRMS (ESI-HR) calc d for C 11 H 13 BrS: , found: ; R f 0.51 (petroleum ether). Minor isomer: 4-Brom-(3-methyl-but-2-enylsulfanyl)-benzene 16-B colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), (m, 1H), 3.51 (d, J = 7.7 Hz, 2H), 1.71 (s, 3H), 1.59 (s, 3H) ppm; 13 C- NMR (125 MHz, CDCl 3 ) δ 136.8, 136.1, 131.7, 131.3, 119.9, 119.0, 32.3, 25.7, 17.8 ppm; IR (Film) ν 2972 (w), 2913 (w), 1472 (s), 1447 (m), 1384 (m), 1218 (w), 1090 (s), 1068 (m), 908 (w), 805 (s), 730 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 258 (22), S17

18 190 (31), 162 (1), 108 (19), 82 (2), 69 (100), 41(35); HRMS (ESI-HR) calc d for C 11 H 13 BrS: , found: ; R f 0.50 (petroleum ether). k) Allylic Substitution with 2-thio-benzylalcohol The product was obtained according to GP-I as a mixture of regio isomeres 15-A/15- B 91:9. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 10:1) in 65 % (135 mg) combined yield. Major isomer: 2-(1,1-Dimethyl-propenylsulfanyl)-benzyl alcohol 15-A colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 1H), (m, 1H), 5.97 (dd, J = 17.2, 10.6 Hz, 1H), 4.92 (dd, J = 10.1, 0.4 Hz, 1H), 4.84 (s, 2H), (m, 1H), 2.02 (bs, 1H), 1.40 (s, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 145.6, 144.7, 138.6, 130.9, 129.4, 128.7, 127.5, 111.8, 64.5, 51.2, 27.6 ppm; IR (Film) ν 3335 (br), 2964 (w), 1633 (w), 1439 (m), 1412 (m), 1377 (m), 1361 (m), 1193 (w), 1116 (s), 1065 (w), 1029 (s), 1002 (s), 912 (s), 753 (s), 685 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 208 (20), 190 (18), 175 (4), 139 (38), 121 (75), 69 (100), 41 (40); HRMS (ESI-HR) calc d for C 12 H 16 OS: , found: ; R f 0.49 (petroleum ether/ethyl acetate 5:1). l) Allylic Substitution with 4-thiophenyl acetamide The product was obtained according to GP-I as a mixture of regio isomeres 19-A/19- B 92:8. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 2:1) in 76 % (178 mg) combined yield. Major isomer: N-(4-(1,1-dimethyl-but-2-enylsulfenyl)-phenyl)-acetamide 19-A S18

19 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 4H), 7.19 (bs, 1H), 5.94 (dd, J = 17.1, 10.6 Hz, 1H), 4.90 (dd, J = 10.3, 1.0 Hz, 1H), 4.70 (dd, J = 17.8, 0.5 Hz, 1H), 2.18 (s, 3H), 1.34 (s, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 168.2, 144.6, 138.2, 131.7, 120.3, 119.2, 111.6, 50.2, 27.4 ppm; IR (Film) ν 3241(w), 3096 (w), 2964 (w), 1659 (s), 1587 (s), 1520 (s), 1489 (s), 1392 (s), 1367 (s), 1312 (s), 1255 (m), 1119 (m), 1016 (m), 994 (m), 901 (m), 824 (s), 753 (w), 685 (w) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 236 (46), 180 (100), 166 (23), 138 (53), 124 (16), 101 (24); HRMS (ESI-HR) calc d for C 13 H 17 NOSNa: , found: ; R f 0.22 (petroleum ether/ethyl acetate 2:1). m) Allylic Substitution with pyridylthiol The product was obtained according to GP-I as a mixture of regio isomeres 21-A/21- B 52:48. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 30:1) in 77 % (137 mg) combined yield. Only the linear product 21-B could be isolated due to isomerization of the branched product 21-A within short time. Minor isomer: 2-(3-Methyl-but-2-enylsulfanyl)-pyridine 21-B 14 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 3.82 (d, J = 7.9 Hz, 2H), 1.73 (s, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 159.6, 149.4, 136.5, 135.9, 122.2, 119.3, 119.1, 28.5, 25.8, 17.9 ppm; IR (Film) ν 2970 (w), 2914 (w), 2360 (w), 2341 (w), 1578 (s), 1556 (m), 1453 (s), 1414 (s), 1124 (s), 756 (s), 724 (w) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 179 (22), 164 (4), 146 (100), 136 (14), 131 (22), 111 (75), 93 (16), 78 (22), 67 (52), 51 (19); R f 0.43 (petroleum ether/ethyl acetate 20:1). S19

20 n) Allylic Substitution with N-methyl-2-mercapto imidazole The product was obtained according to GP-I as a mixture of regio isomeres 22-A/22- B 64:36. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 2:1) in 79 % (147 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether/ethyl acetate 3:1). Major isomer: 2-(1,1-Dimethyl-propenylsulfanyl)-1-methyl-1H-imidazole 22-A colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ 6.83 (d, J = 2.27 Hz, 1H), 6.65 (d, J = 2.64 Hz, 1H), 6.34 (dd, J = 17.4, 10.6 Hz, 1H), (m, 2H), 3.58 (s, 3H), 1.89 (s, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 161.5, 142.4, 116.9, 114.7, 113.8, 61.7, 35.0, 26.1 ppm; IR (Film) ν 2976 (w), 2929 (w), 1445 (m), 1404 (m), 1371 (s), 1286 (m), 1205 (s), 1182 (m), 1139 (m), 1088 (w), 927 (w), 709 (m), 670 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 182 (57), 167 (2), 149 (5), 136 (3), 114 (100), 81 (5), 69 (9), 41 (14); HRMS (ESI-HR) calc d for C 9 H 14 N 2 S: , found: ; R f 0.44 (petroleum ether/ethyl acetate 1:1). Minor isomer: 2-(3-methyl-but-2-enylsulfanyl)-1-methyl-1H-imidazole 22-B colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ 7.09 (d, J = 1.6 Hz, 1H), 6.93 (d, J = 1.3 Hz, 1H), (m, 1H), 3.66 (d, J = 8.3 Hz, 2H), 3.62 (s, 3H), 1.69 (s, 3H), 1.52 (s, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 141.6, 137.3, 129.1, 122.2, 118.8, 33.5, 33.3, 25.7, 17.4 ppm; IR (Film) ν 2969 (w), 2928 (w), 2358 (m), 2339 (m), 1454 (s), 1376 (m), 1280 (s), 1220 (w), 1123 (m), 914 (w), 844 (w), 745 (m), 688 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 182 (12), 167 (1), 149 (7), 136 (6), 114 (100), 99 (1), 81 S20

21 (6), 72 (14), 53 (4); HRMS (ESI-HR) calc d for C 9 H 15 N 2 S: , found: ; R f 0.41 (petroleum ether/ethyl acetate 1:1). o) Allylic Substitution with hexadecylthiol The product was obtained according to GP-I as a mixture of regio isomeres 23-A/23- B 85:15. The product was isolated by column chromatography on silica (petroleum ether) in 88 % (278 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether). Major isomer: 3-Hexadecyl-3-methyl-but-1-ene 23-A colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ 5.85 (dd, J = 17.3, 10.5 Hz, 1H), (m, 2H), 2.36 (t, J = 7.4 Hz, 2H), (m, 2H), 1.36 (s, 6H), 1.25 (s, 28H), 0.87 (t, J = 6.7 Hz, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 145.0, 111.0, 46.2, 31.9, 29.8, 29.7, 29.6, 29.5, 29.4, 29.3, 29.2, 29.0, 27.5, 22.7, 14.1 ppm; IR (Film) ν 2921 (s), 2852 (s), 1465 (m), 1376 (w), 1362 (w), 1126 (m), 994 (w), 908 (m), 735 (m), 688 (w) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 326 (20), 311 (3), 299 (2), 257 (47), 213 (2), 171 (1), 129 (1), 101 (6), 69 (100), 55 (8), 41 (13); HRMS (ESI-HR) calc d for C 21 H 42 S: , found: ; R f 0.52 (petroleum ether). Minor isomer: 1-Hexadecyl-3-methyl-but-2-ene 23-B 15 S colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 1H), 3.13 (d, J = 7.8 Hz, 2H), 2.45 (t, J = 7.4 Hz, 2H), 1.74 (s, 3H), 1.67 (s, 3H), (m, 2H), 1.26 (m, 28H), 0.88 (t, J = 6.7 Hz, 3H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 134.9, 120.9, 31.9, 31.3, 29.9, 29.8, 29.7, 29.6, 29.5, 29.4, 29.3, 29.2, 29.1, 25.7, 22.7, 17.7, 14.1 ppm; S21

22 IR (Film) ν 2921 (s), 2852 (s), 2360 (w), 2341 (w), 1465 (m), 1376 (w), 844 (w), 806 (w), 720 (w) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 326 (46), 311 (2), 257 (60), 213 (2), 171 (2), 129 (2), 101 (12), 83 (5), 69 (100), 55 (9), 41 (17); HRMS (ESI-HR) calc d for C 21 H 42 S: , found: ; R f 0.50 (petroleum ether). p) Allylic Substitution with 2-phenylethanethiol The product was obtained according to GP-I as a mixture of regio isomeres 24-A/24- B 92:8. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 40:1) in 91 % (187 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether/ethyl acetate 40:1). Major isomer: 2-(1-Methyl-but-2-enylsulfanyl-ethyl)-benzene 24-A Colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), 5.86 (dd, J = 17.3, 10.5 Hz, 1H), (m, 2H), (m, 2H), (m, 2H), 1.38 (s, 6H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 144.8, 141.0, 128.4, 126.3, 111.3, 46.6, 36.2, 30.7, 27.5 ppm; IR (Film) ν 3028 (w), 2963 (m), 2923 (m), 2863 (w), 2360 (m), 2341 (m), 1633 (w), 1496 (m), 1454 (m), 1362 (m), 1125 (s), 995 (w), 911 (s), 734 (m), 697 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 206 (47), 191 (1), 138 (20), 115 (8), 104 (18), 91 (27), 77 (6), 69 (100), 53 (2), 41 (26) ; HRMS (ESI-HR) calc d for C 13 H 18 S: , found: ; R f 0.48 (petroleum ether/ethyl acetate 20:1). Minor isomer: 2-(3-Methyl-but-2-enylsulfanyl-ethyl)-benzene 24-B Colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), (m, 1H), 3.16 (d, J = 7.6 Hz, 2H); (m, 2H), (m, 2H), 1.76 (s, 3H); 1.67 (s, 3H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 140.9, 135.4, 128.5, 126.3, 120.7, 36.5, 32.7, 29.7, 25.7, 17.8 ppm; IR (Film) ν 3022 (w), 2911 (w), 2360 (m), 2330 (m), 1508 S22

23 (w), 1429 (w), 1377 (w), 835 (w), 733 (m), 699 (s), 669 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 206 (74), 191 (1), 138 (19), 115 (8), 104 (21), 91 (33), 77 (8), 69 (100), 51 (3), 41 (27); HRMS (ESI-HR) calc d for C 13 H 18 S: , found: ; R f 0.46 (petroleum ether/ethyl acetate 20:1). q) Allylic Substitution with 2-mercaptoethanol The product was obtained according to GP-I as a mixture of regio isomeres 25-A/25- B 92:8. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 3:1) in 69 % (101 mg) combined yield. Major isomer: 2-(2-Methyl-But-2-enyl)-ethanol 25-A yellow oil; R f 0.32 (petroleum ether/ethyl acetate 3:1); 1 H-NMR (300 MHz, CDCl 3 ) δ 5.86 (dd, J = 17.3, 10.6 Hz, 1H), (m, 2H), 3.69 (t, J = 6.2 Hz, 2H), 2.63 (t, J = 6.2 Hz, 2H), 1.39 (s, 6H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 144.7, 111.8, 61.4, 32.7, 27.7 ppm; IR (Film) ν 3351 (b), 2964 (m), 2924 (m), 2867 (w), 1633 (w), 1456 (m), 1413 (m), 1378 (m), 1363 (m), 1125 (s), 1043 (s), 1001 (s), 912 (s), 696 (m) cm - 1 ; GC/MS (EI, 70 ev) m/z (%) = 146 (33), 131 (1), 101 (8), 85 (1), 69 (100), 59 (3), 53 (6), 41 (47); HRMS (ESI-HR) calc d for C 7 H 14 OS: , found: ; R f 0.32 (petroleum ether/ethyl acetate 3:1). r) Allylic Substitution with 2-mercapto-glycolic acid methylester The product was obtained according to GP-I as a mixture of regio isomeres 26-A/26- B 91:9. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 10:1) in 62 % (108 mg) combined yield. Major isomer: 1-Methyl-but-2-enylsulfanyl-acetic acid methyl ester 26-A S23

24 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ 5.82 (dd, J = 17.3, 10.5 Hz, 1H), (m, 2H), 3.71 (s, 3H), 3.17 (s, 2H), 1.39 (s, 6H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 171.4, 143.7, 112.5, 52.3, 47.4, 31.9, 27.1 ppm; IR (Film) ν 2966 (w), 1735 (s), 1435 (m), 1380 (w), 1364 (w), 1271 (s), 1121 (s), 1005 (m), 915 (m), 688 (w) cm - 1 ; GC/MS (EI, 70 ev) m/z (%) = 174 (45), 159 (1), 143 (8), 115 (3), 101 (46), 84 (10), 69 (100), 53 (5), 41 (37); HRMS (ESI-HR) calc d for C 8 H 14 O 2 S: , found: ; R f 0.39 (petroleum ether/ethyl acetate 10:1). s) Allylic Substitution with 3-mercaptopropyl trimethoxysilan The product was obtained according to GP-I as a mixture of regioisomeres 27-A/27- B 93:7. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 10:1) in 76 % (201 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether/ethyl acetate 10:1). Major isomer: Trimethoxy-1-(3-(1,1-dimethyl-allylthio)propyl)silan 27-A colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ 5.85 (dd, J = 17.3, 10.6 Hz, 1H), 4.99 (dd, J = 10.5, 1.2 Hz, 1H), 4.93 (dd, J = 17.4, 1.2 Hz, 1H), 3.56 (s, 9H), 2.40 (t, J = 7.4 Hz, 2H), (m, 2H), 1.36 (s, 6H), (m, 2H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 145.0, 111.0, 50.5, 46.3, 32.1, 27.5, 23.2, 9.0 ppm; IR (Film) ν 2942 (m), 2840 (m), 2360 (m), 2342 (m), 1457 (w), 1191 (m), 1086 (s), 912 (w), 814 (m), 766 (w) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 287 (100), 273 (5), 250 (13), 233 (11), 216 (14), 165 (18), 151 (16), 133 (8), 119 (2) ; HRMS (ESI-HR) calc d for C 11 H 24 O 3 SSiNa: , found: ; R f 0.19 (petroleum ether/ethyl acetate 10:1). Minor isomer: Trimethoxy-1-(3-(3-methyl-but-2-enylthio)propyl)silan 27-B S24

25 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 1H), 3.57 (s, 9H), 3.13 (d, J = 7.8 Hz, 2H), 2.49 (t, J = 7.4 Hz, 2H), (m, 2H), 1.74 (s, 3H), 1.66 (s, 3H), (m, 2H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 135.0, 120.8, 50.5, 34.2, 29.3, 25.7, 23.0, 17.7, 8.7 ppm; IR (Film) ν 2941 (m), 2839 (m), 2361 (m), 2342 (m), 1191 (m), 1086 (s), 811 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 287 (100), 273 (5), 165 (15), 151 (21), 133 (15) ; HRMS (ESI-HR) calc d for C 11 H 24 O 3 SSiNa: , found: ; R f 0.17 (petroleum ether/ethyl acetate 10:1). t) Allylic Substitution of allyl methyl carbonate with benzyl mercaptan The product was obtained according to GP-I. It was isolated by column chromatography on silica (petroleum ether) in 95 % (156 mg) yield. Benzyl allyl sulfide colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), 5.80 (ddt, J = 16.8, 12.1, 6.0 Hz, 1H), (m, 2H), 3.66 (s, 2H), 3.04 (d, J = 7.2 Hz, 2H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 138.3, 134.2, 129.0, 128.5, 126.9, 117.3, 34.9, 34.1, 26.9 ppm; IR (Film) ν 3029 (w), 2912 (w), 1634 (w), 1494 (m), 1453 (m), 1227 (w), 1070 (m), 990 (m), 742 (m), 700 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 164 (26), 122 (20), 105 (3), 91 (100), 77 (5), 65 (8), 45 (8); R f 0.39 (petroleum ether). u) Allylic Substitution of 2-butenyl methyl carbonate with benzyl mercaptan The product was obtained according to GP-I as a mixture of regio isomeres 32-A/32- B >99:<1. The product was isolated by column chromatography on silica (petroleum ether) in 94 % (168 mg) combined yield. Major isomer: Benzyl crotyl sulphide 32-A 16 S25

26 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ , m, 5H), (m, 2H), 3.66 (s, 3H), (m, 2H), (m, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 138.6, 129.0, 128.5, 128.4, 126.9, 126.8, 35.0, 33.3, 17.7 ppm; IR (Film) ν 3026 (w), 2915 (w), 1737 (m), 1494 (m), 1453 (m), 1417 (w), 1223 (w), 1069 (w), 963 (s), 931 (m), 764 (m), 696 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 178 (45), 124 (21), 91 (100), 77 (5), 65 (15), 55 (14), 45 (16); HRMS (ESI-HR) calc d for C 11 H 14 S: , found: ; R f 0.32 (petroleum ether). v) Allylic Substitution of 3-buten-2-yl methyl carbonate with benzyl mercaptan The product was obtained according to GP-I as a mixture of regio isomeres 32-B/32- A 95:5. The product was isolated by column chromatography on silica gel (petroleum ether) in 88 % (157 mg) combined yield. Major isomer: Benzyl-1-methylallyl sulfide 32-B 16 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ m, 5H), (m, 1H), (m, 2H), (m, 2H), 3.21 (app. quint., J = 7.3 Hz, 1H), 1.31 (s, 3H), 1.28 (s, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 140.5, 138:7, 128:9, 128:5, 126:8, 114.5, 42.5, 35.2, 20.0 ppm; IR (Film) ν 3029 (w), 2965 (w), 2925 (w), 1633 (w), 1494 (m), 1452 (m), 1414 (w), 1220 (w), 1071 (w), 1028 (m), 990 (m), 912 (s), 722 (s), 696 (s), 564 (m) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 178 (17), 163 (1), 145 (1), 122 (19), 91 (100), 77 (11), 65 (21), 55 (20); R f 0.31 (petroleum ether). w) Allylic Substitution of 3-methyl-but-2-enyl methyl carbonate with benzyl mercaptan S26

27 The product was obtained according to GP-I as a mixture of regio isomeres 3-B/3-A 96:4. The product was isolated by column chromatography on silica (petroleum ether) in 80 % (154 mg) combined yield. Major regioisomer: Benzyl 3-methylbut-2-enyl sulphide 3-B 17 colourless oil; R f 0.62(petroleum ether/ethyl acetate 20:1); 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), (m, 1H), 3.68 (s, 2H), 3.05 (d, J = 7.8 Hz, 2H), 1.73 (s, 3H), 1.58 (s, 3H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 138.6, 135.5, 128.9, 128.4, 126.8, 120.4, 35.7, 29.1, 25.7, 17.8 ppm; IR (Film) ν 3028 (w), 2972 (w), 2913 (w), 1494 (m), 1452 (m), 1376 (m), 1333 (w), 1070 (w), 840 (m), 765 (m), 696 (s), 563 (w) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 192 (32), 177 (2), 143 (1), 136 (4), 124 (25), 101 (19), 91 (100), 77 (10), 69 (85), 59 (12), 51 (11); R f 0.62 (petroleum ether/ethyl acetate 20:1). x) Allylic Substitution of 1-methyl-but-2-enyl methyl carbonate with benzyl mercaptan The product was obtained according to GP-I. It was isolated by column chromatography on silica (petroleum ether) in 87 % (167 mg) yield. Benzyl-4-pent-2enyl sulphide 33 S27

28 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), (m, 2H), 3.57 (d,j = 3.0 Hz, 2H), (m, 1H), 1.65 (d, J = 6.1Hz, 3H), 1.20 (d, J = 6.9 Hz, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 138.9, 133.7, 128.9, 128.4, 126.8, 125.8, 41.8, 35.3, 20.6, 17.6 ppm; IR (Film) ν 2967 (w), 2918 (w), 1494 (m), 1451 (m), 1258 (m), 1018 (m), 963 (s), 695 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 192 (78), 177 (1), 124 (12), 101 (18), 91 (50), 69 (100), 41 (24); HRMS (ESI-HR) calc d for C 12 H 16 S: , found: ; R f 0.54 (petroleum ether). y) Allylic Substitution of cinnamyl i-butyl carbonate with benzyl mercaptan The product was obtained according to GP-I as a mixture of regio isomeres 34-A/34- B >99:<1. The product was isolated by column chromatography on silica (petroleum ether) in 82 % (197 mg) combined yield. Major isomer: Benzyl cinnamyl sulfide 34-A 13 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 10H), 6.40 (d, J = 15.7 Hz, 1H), 6.17 (dt, J = 15.1, 7.6 Hz, 1H), 3.70 (s, 2H), 7.16 (d, J = 7.2 Hz, 2H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 132.5, 129.0, 128.6, 128.5, 127.6, 127.0, 126.3, 125.8, 35.1, 33.7 ppm; IR (Film) ν 3026 (w), 1700 (w), 1676 (w), 1493 (m), 1452 (m), 1071 (m), 1027 (m), 963 (m), 748 (s), 694 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 240 (37), 214 (5), 181 (1), 149 (9), 117 (100), 91 (44), 77 (6), 65 (5), 45 (5); R f 0.15 (petroleum ether). z) Allylic Substitution of 1-phenyl-but-2-enyl i-butyl carbonate with benzyl mercaptan S28

29 The product was obtained according to GP-I as a mixture of regio isomeres 35-A/35- B 91:9. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 40:1) in 80 % (202 mg) combined yield. Major isomer: Benzyl-(1-phenyl-but-2-enyl)-sulfide 35-A yellow oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), 6.33 (d, J = 15.7 Hz, 1H), 6.08 (dd, J = 15.7, 9.0 Hz, 1H), 3.68 (s, 2H), (m, 1H), 1.38 (d, J = 6.8 Hz, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 138.6, 136.7, 132.2, 129.9, 128.9, 128.6, 128.5, 127.5, 126.9, 126.3, 42.2, 35.4, 20.5 ppm; IR (Film) ν 2954 (m), 2922(m), 2853 (m), 1494 (w), 1453 (m), 963 (m), 748 (s), 694 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 254 (11), 246 (1), 163 (1), 131 (100), 115 (11), 103 (3), 91 (47), 77 (12), 57 (12), 43 (11); HRMS (ESI-HR) calc d for C 17 H 18 S: , found: ; R f 0.38 (petroleum ether/ethyl acetate 40:1). aa) Allylic Substitution of cyclohex-2-enyl i-butyl carbonate with benzyl mercaptan The product was obtained according to GP-I. It was isolated by column chromatography on silica (petroleum ether) in 59 % (121 mg) yield. (Cyclohex-2-enylsulfanylmethyl)-benzene colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), (m, 1H), 5.65 (ddt, J = 9.9, 3.8, 1.9 Hz, 1H), 3.76 (s, 2H), (m, 1H), (m, S29

30 2H), (m, 3H), (m, 1H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 138.7, 129.9, 128.9, 128.5, 127.5, 126.9, 40.0, 35.5, 29.0, 25.0 ppm; IR (Film) ν 3026 (w), 2929 (w), 1494 (m), 1453 (m), 1203 (w), 1069 (m), 1028 (m), 747 (s), 696 (s) cm - 1 ; GC/MS (EI, 70 ev) m/z (%) = 204 (14), 123 (4), 113 (5), 91 (50), 80 (100), 65 (11), 53 (8), 45 (15), 39 (9); R f 0.36 (petroleum ether). bb) Allylic Substitution of 1-benzyloxyprop-2-enyl i-butyl carbonate with benzyl mercaptan The product was obtained according to GP-I as a mixture of regio isomeres 37-A/37- B 90:10. The product was isolated by column chromatography on silica (petroleum ether/ethyl acetate 40:1) in 79 % (224 mg) combined yield. Major isomer: 4-Benzyloxy-3-benzylsulfanyl-buten 37-A yellow oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 10H), (m, 1H), (m, 2H), 4.51 (s, 2H), (m, 2H), 3.57 (dd, J = 6.3, 1.4 Hz, 2H), 3.39 (dt, J = 8.6, 6.5 Hz, 1H) ppm; 13 C-NMR (75 MHz, CDCl 3 ) δ 138.3, 138.0, 136.3, 129.0, 128.5, 128.4, 127.7, 127.6, 127.0, 117.1, 73.1, 72.0, 47.7, 34.9 ppm; IR (Film) ν 3029 (w), 2919 (w), 2852 (w), 1720 (w), 1495 (w), 1453 (m), 1102 (s), 1071 (m), 1027 (m), 969 (w), 737 (m), 697 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 284 (5), 193 (2), 176 (2), 160 (6), 123 (4), 105 (2), 91 (100), 65 (8), 45 (4); HRMS (ESI-HR) calc d for C 18 H 20 OSNa: , found: ; R f 0.40 (petroleum ether/ethyl acetate 20:1). cc) Allylic Substitution of geranyl i-butyl carbonate with benzyl mercaptan The product was obtained according to GP-I as a mixture of regio isomeres 29-B/29- A 90:10. The product was isolated by column chromatography on silica (petroleum ether) in 76 % (199 mg) combined yield. S30

31 Major isomer: 3,7-Dimethyl-octa-2,6-dienyl-benzylsulfide 29-B 18 colourless oil; 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), (m, 1H), (m, 1H), 3.60 (s, 2H), 2.98 (d, J = 7.6 Hz, 2H), (m, 4H), 1.61 (s, 3H), 1.53 (s, 3H), 1.49 (s, 3H) ppm; 13 C-NMR (125 MHz, CDCl 3 ) δ 139.1, 138.7, 131.7, 128.9, 128.4, 126.8, 124.1, 120.4, 39.6, 65.5, 29.0, 26.5, 25.8, 17.8, 16.2 ppm; IR (Film) ν 2966 (w), 2915 (m), 2854 (w), 1494 (w), 1452 (m), 1377 (w), 1232 (w), 1070 (w), 839 (w), 767 (w), 697 (s) cm -1 ; GC/MS (EI, 70 ev) m/z (%) = 260 (38), 214 (2), 191 (3), 169 (29), 136 (22), 123 (20), 91 (100), 81 (15), 69 (73) 41 (24); HRMS (ESI-HR) calc d for C 17 H 24 S: , found: ; R f 0.42 (petroleum ether). dd) Allylic Substitution of (R)-28 with benzyl mercaptan The product was obtained according to GP-I as a mixture of regio isomeres 29-A/29- B 88:12. The product was isolated by column chromatography on silica (petroleum ether) in 76 % (198 mg) combined yield. The regioisomers were separated by means of semi-preparative HPLC (petroleum ether). The enantiomeric ratio was determined by means of HPLC: DAICEL CHIRALCEL OJ, n-heptane/iso-propyl alcohol 99:1, flow rate: 1.0 ml/min, detector: 220 nm, R (t R = 10.5 min), S (t S = 12.7 min). (R)-Linalyl-benzyl sulfide 29-A colourless oil; [a] 20 D (c = 0.4, CHCl 3 ); 1 H-NMR (300 MHz, CDCl 3 ) δ (m, 5H), 5.88 (dd, J = 17.3, 10.7 Hz, 1H), 5.14 (dd, J = 10.4, 0.8 Hz, 1H), (m, 1H), 5.01 (dd, J = 17.7, 0.8 Hz, 1H), 3.57 (d, J = 2.3 Hz, 2H), (m, 2H), 1.67 (s, 3H), (m, 2H), 1.59 (s, 3H), 1.38 (s, 3H) ppm; 13 C-NMR (125 MHz, S31