SUPPLEMENTARY INFORMATION

In the format provided by the authors and unedited. SUPPLEMENTARY INFORMATION DOI: 10.1038/NCHEM.2789 Catalytic asymmetric trifluoromethylthiolation via enantioselective [2,3]-sigmatropic rearrangement of sulfonium ylides Zhikun Zhang, Zhe Sheng, Weizhi Yu, Guojiao Wu, Rui Zhang, Wen-Dao Chu, Yan Zhang, and Jianbo Wang* Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China. Email: wangjb@pku.edu.cn CONTENTS 1. General... 2 2. Synthesis of substrates.. 2 3. General procedure for Rh(II)-catalyzed [2,3]-sigmatropic rearrangement... 4 4. Mechanistic studies...... 5 4.1. General procedure for the reactions of diazoesters with diallyl sulfide. 5 4.2. Reactivity comparison between allylic trifluoromethyl sulfide 1 and allylic methyl sulfide 1'. 6 5. Cu(I)-catalyzed [2,3]-sigmatropic rearrangement....... 6 5.1. Preparation of the Box chiral ligands...7 5.2. Reaction condition optimization 7 Supplementary Table 1. Optimization of the reaction conditions with Cu(I)/L*-catalysts.. 7 5.3. General procedure for Cu(I)-catalyzed [2,3]-sigmatropic rearrangement... 9 5.4. Mechanistic studies for Cu(I)-catalyzed reaction.. 9 5.4.1. Cu(I)/L*-catalyzed reaction with diallyl sulfide 13 9 5.4.2. Cu(I)/L*-catalyzed reaction with diallyl sulfide 11 10 6. Characterization data for the products... 11 7. X-ray structure of 8 and 10j.. 32 7.1. Solid state structure of 8 32 7.2. Solid state structure of 10j. 39 8. References... 43 9. 1 H, 13 C, 19 F NMR spectra and HPLC data of the products... 44 NATURE CHEMISTRY www.nature.com/naturechemistry 1 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.

1. General All the reactions were performed with a dried reaction tube. All solvents were distilled under nitrogen atmosphere prior to use. DCM, pentane and p-xylene were distilled over CaH 2. For chromatography, 200-300 mesh silica gel (Qingdao, China) was employed. Chiral Rh(II) catalysts and Cu(CH 3 CN) 4 PF 6 were commercially available and some chiral ligands were commercially available from Daicel. 1 H and 13 C NMR spectra were recorded at 400 MHz and 100 MHz with Brucker ARX 400 spectrometer. 19 F NMR was recorded at 376 MHz with Brucker ARX 400 spectrometer. Chemical shifts are reported in ppm using tetramethylsilane (0) as internal standard when using CDCl 3 as solvent for 1 H NMR spectra. For 13 C NMR spectra, CDCl 3 was used as the internal standard with chemical shift at 77 ppm. For 19 F NMR spectra, CFCl 3 was used as the reference with chemical shift at 0 ppm. The data for NMR spectra were reported as following: chemical shifts (δ) were reported in ppm, and coupling constants (J) were reported in Hertz (Hz). The following abbreviations were used to symbolize the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad. IR spectra were recorded with a Thermo Electron Corporation Nicolet AVATAR 330 FT-IR spectrometer, HRMS was detected through Thermo scientific Q exactive GC-MS, optical rotations were measured with Perkin Elemer Model 341LC Polarimeter, ee values were measured with HPLC (Agilent Technologies 1200 series) with Daicel chiral column, eluted with n-hexane and isopropanol. 2. Synthesis of substrates Allylic trifluoromethyl sulfide (1): 1 Under a nitrogen atmosphere, CuSCN (4.88 g,40 mmol), S 8 (25 g, 98 mmol), KF (18.56 g, 320 mmol) were successively added to a dry 500 ml reaction Schlenk flask. The reaction flask was degassed three times with nitrogen, and dry DMF (80 ml) was added using a syringe. Allylic chloride (6.08 g, 80 mmol) was added through a syringe, then TMSCF 3 (34 g, 240 mmol) was added dropwise over 5 min via a syringe at 0 o C. After stirring at 0 o C for 12 h, the reaction was heated at 45 o C for 4 h. (Caution: Large amount of TMSF will be evaporated, make sure the system is NOT CLOSED). The reaction mixture was filtered through silica gel, and the filtrate was collected. The filtrate was subjected to fractional distillation twice to obtain the desired product. In the first fractional distillation, all fractions were collected before 120 o C. In the second fractional 2

distillation, the fractions between 65 o C and 68 o C were collected as the final product. NMR analysis indicated that the product was still contaminated by small amount of TMSF, but it would not have influence on the [2,3]-sigmatropic rearrangement reaction. The yield was 40% (4.19 g). 1 H NMR (CDCl 3, 400 MHz) δ 5.94-5.84 (m, 1H), 5.29 (d, J = 16.9 Hz, 1H), 5.20 (d, J = 10.0 Hz, 1H), 3.53 (d, J = 7.0 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 132.3, 130.8 (q, J = 306.6 Hz, 1C), 119.2, 32.8; 19 F NMR (CDCl 3, 376 MHz) δ -41.9 (s, 3F). The NMR is consistent with those reported in ref. 1. Propargyl trifluoromethyl sulfide (2): 2 Under nitrogen atmosphere, AgSCF 3 (6.05 g, 28.95 mmol) was added to a dried 50 ml Schlenk bottle with a magnetic stir. The reaction flask was degassed and backfilled three times with nitrogen. Then benzyl cyanide (10 ml) and propargyl bromide (3.13 g, 26.3 mmol) were added to the flask, successively. At last, the flask was immersed in 80 o C oil bath for 12 h until the AgSCF 3 was disappeared as judged by 19 F NMR. The reaction mixture was filtered through silica gel, and the filtrate was collected. Then fraction between 68 o C to 70 o C was collected through fractional distillation. And the product was got in 46 % yield (2.10 g). 1 H NMR (CDCl 3, 400 MHz) δ 3.65 (d, J = 2.7 Hz, 2H), 2.33 (t, J =2.7 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 130.2 (q, J = 307.4 Hz, 1C), 77.0, 72.8, 18.2 (q, J = 3.3 Hz, 1C); 19 F NMR (CDCl 3, 376 MHz) δ -42.1 (s, 3F). reaction. 3 Diazo compounds: All the diazo compounds was prepared by the classic diazo transfer Ester 8: Chiral compounds 3f (33.6 mg, 0.088 mmol) was transferred to a 10 ml dried Schenk flask, then it was degassed and backfilled three times with nitrogen. THF (1.0 ml) was added through a syringe, and then 4.0 mg LiAlH 4 (0.106 mmol) was added slowly at 0 o C. After stirring at 0 o C for 1 h, the reaction was quenched with water, then it was extracted with ethyl ether. The solvent was removed under reduced pressure and the crude product was 3

purified by chromatography with silica gel to afford the intermediate alcohol (13.0 mg, 44%). The alcohol was transferred to 10 ml dried Schenk flask, then 1.0 ml dichloromethane was added through a syringe and 4-nitrobenzoyl chloride (13 mg) was added to the flask. After the alcohol was disappeared as judged by 1 H NMR, the reaction solvent was evaporated through rotary evaporator to leave a crude product which was purified to afford ester 8 in 99% yield as a white solid (18.5 mg) with silica gel. Cinnamyl trifluoromethyl sulfide (11): 11 was synthesized according to the literature procedure. 4 A colourless oil was obtained (1.76 g, 81%). Phenylpropyl trifluoromethyl sulfide (15): 15 was synthesized according to literature, 5 colourless oil was obtained (0.75 g, 68% yield for two steps). 3. General procedure for Rh(II)-catalyzed [2,3]-sigmatropic rearrangement For aryldiazoacetates: Under a nitrogen atmosphere, pentane (2-4 ml), allyl trifluoromethyl sulfide 1 (31 mg, 0.22 mmol, 1.1 equiv.) or propargyl trifluoromethyl sulfide 6 (34 mg, 0.24 mmol, 1.2 equiv.) were successively added to a dry 10 ml Schlenk reaction tube. To the solution was then added the aryldiazoacetate 2 (0.2 mmol, 1.0 equiv.), and the reaction tube was immersed in -30 o C bath. After 5 min, a solution of Rh 2 (S-DOSP) 4 (0.5 mol%) in 0.25 ml pentane was added dropwise to the reaction tube. The reaction solution was stirred for 12 h. In case the typical color of diazo compounds did not disappear, an additional solution of Rh 2 (S-DOSP) 4 (0.5 mol%) in 0.25 ml pentane was added. The reaction was terminated when the color of diazo compounds completely disappeared. The solvent was removed with rotary evaporator under reduced pressure to leave a crude mixture, which was purified by preparative thin-layer chromatography to afford pure product. For diazo compounds 2e, 2f, 2i, 2k and 2l, 4 ml pentane was used; in all the other cases 2 ml pentane was used. For vinyldiazoacetate: Under a nitrogen atmosphere, pentane (2-6 ml), allyl trifluoromethyl sulfide 1 (28 mg, 0.20 mmol, 1.0 equiv.) or propargyl trifluoromethyl sulfide 4

6 (28 mg, 0.20 mmol, 1.0 equiv.) were successively added to a dry 10 ml Schlenk reaction tube. Then the vinyldiazoacetate 4 (0.24 mmol, 1.2 equiv.) for 1 and vinyldiazoacetate 4 (0.26 mmol, 1.3 equiv.) for 6 was added to the solution. Then the reaction tube was immersed in -30 o C bath. After 5 min, a solution of Rh 2 (S-DOSP) 4 (0.5 mol%) in 0.25 ml pentane was added dropwise to the reaction tube. The reaction was stopped when the color of diazo compound disappeared. The solvent was removed with rotary evaporator under reduced pressure to leave a crude mixture, which was purified by preparation thin-layer chromatography to afford pure product. For diazo compounds 4c, 4e, 4f, 4g, 4h, and 4m, 4 ml pentane was used; for 4i and 4l, 6 ml pentane was used, in all the other cases 2 ml pentane was used. The corresponding racemic products were prepared with Rh 2 (OAc) 4 (1 mol%) as the catalyst. The purification processes were the same as those for the chiral products. 4. Mechanistic studies 4.1. General procedure for the reactions of diazoesters with diallyl sulfide For aryl diazoesters 2a reacted with diallyl sulfide 13 in the presence of different Rh 2 L 4 catalysts: Under a nitrogen atmosphere, Rh 2 (S-PTTL). 4 2EtOAc, Rh 2 (S-BTPCP) 4, Rh 2 (S-PTAD) 4, Rh 2 (5S-MEPY) 4, or Rh 2 (4S-MEAZ) 4 (0.001 mmol, 1.0% mol) was added to a dry 10 ml Schlenk reaction tube, pentane (0.5 ml), dichloromethane (0.5 ml), diallyl sulfide 13 (11 mg, 0.1 mmol, 1.0 equiv.) was added successively. At 0 o C, diazoacetate 2a (19 mg, 0.1 mmol, 1.0 equiv.) was added to the reaction tube. After that, the reaction tube was reacted for about 24 h at 0 o C until the colour of diazoacetate was disappeared. The solvent was removed with rotary evaporators to leave a crude mixture, which was purified by preparation thin-layer chromatography to afford pure product 14a-1, 14a-2, 14a-3, 14a-4, and 14a-5. For Rh 2 (S-DOSP) 4 -catalyzed reaction of diazoesters 2a, 2e, 2j, 4a or 4j with diallyl sulfide 13: Under a nitrogen atmosphere, diazoesters 2a, 2e, 2j, 4a or 4j (0.13 mmol, 1.3 equiv) was added to a dry 10 ml Schlenk reaction tube, pentane (2 ml for 2a, 2e, 2j and 4a, 4 ml for 4j), diallyl sulfide 13 (11 mg, 0.1 mmol, 1.0 equiv.) was added successively. At 0 o C, Rh 2 (S-DOSP) 4 (1.9 mg, 0.001 mmol, 1.0% mol) solution in 0.2 ml pentane was added to the reaction tube. After that, the reaction tube was reacted for about 24 h at 0 o C until the colour of diazoacetate was disappeared. The solvent was removed with rotary evaporator to leave a 5

crude mixture, which was purified by preparative thin-layer chromatography to afford pure product 14a, 14b, 14c, 14d, 14e. 4.2. Reactivity comparison between allylic trifluoromethyl sulfide 1 and allylic methyl sulfide 1 ' : When we use allylic methyl sulfide to replace the allylic trifluoromethyl sulfide to conduct this transformation, at -30 o C, there was no product was detected, and at 0 o C, only trace amount of product was detected. When the reaction was conduct at 30 o C for 72 hours, the product 3a ' was isolated in 50 mg (0.2 mmol scale), 99% yields. However, the e.e. value was 0% (conditions: OJ-H, Hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm). 1 H NMR (CDCl3, 400 MHz) δ 7.41-7.38 (m, 2H), 7.36-7.32 (m, 2H), 7.28-7.24 (m, 1H), 5.75-5.64 (m, 1H), 5.03-4.97 (m, 2H), 4.26 (q, J = 7.1 Hz, 2H), 2.93-2.83 (m, 2H), 1.93 (s, 3H), 1.27 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 171.9, 138.6, 132.9, 128.1, 127.7, 127.2, 118.5, 61.4, 59.8, 42.5, 14.0, 13.1. 6 Further, the reaction was conducted in the presence of allylic trifluoromethyl sulfide 1 and allylic methyl sulfide 1 '. The dediazoniation was totally suppressed and no product 3a was detected. When we mix Rh 2 (S-DOSP) 4 with sulfide 1 ', the reaction system turned to pink immediately, which means the coordination between sulfide 1 and rhodium is easy. However, when we mix Rh 2 (S-DOSP) 4 with sulfide 1, the colour was slightly changed from green to deep green. Further, we mixed sulfide with 20% mol Rh 2 (S-DOSP) 4, the system was detected through 19 F NMR, no changed signal was detected which means the coordination between rhodium and sulfide 1 is not as strong as that of sulfide 1 '. According to the experiment above, we suggested the owing to the weak coordination between sulfide 1 with rhodium making the reaction undergo at very low temperature to realize high enantioselectivity. 5. Cu(I)-catalyzed [2, 3]-sigmatropic rearrangement 6

5.1. Preparation of the Box chiral ligands The ligands used in this part work was synthesized according to the reference procedures. 7 5.2. Reaction condition optimization Supplementary Table 1. Optimization of the reaction conditions with Cu(I)/L*-catalysts 7

Entry * R L * T ( o C) Solvent Yield (%) e.e. (%) 1 Me L1 30 DCM 32 10 2 Me L2 30 DCM 44 0 3 Me L3 30 DCM 36 0 4 Me L4 30 DCM 58 < 5 5 Me L5 30 DCM 0-6 Me L6 30 DCM 50 26 7 Me L7 30 DCM 29 < 5 8 Me L8 30 DCM 22 < 5 9 Me L9 30 DCM 42 11 10 Et L6 30 DCM 31 37 11 i Pr L6 30 DCM 34 43 12 t Bu L6 30 DCM 44 56 13 Ph L6 30 DCM 18 11 14 t Bu L9 30 DCM 30 62 15 t Bu L10 30 DCM 26 66 16 t Bu L11 30 DCM 25 60 17 t Bu L12 30 DCM - 85 8

18 t Bu L13 30 DCM 53 89 19 t Bu L14 30 DCM - 83 20 t Bu L15 30 DCM - 88 21 t Bu L16 30 DCM - 83 22 t Bu L17 30 DCM - 86 23 t Bu L18 30 DCM - 70 24 t Bu L19 30 DCM - 82 25 t Bu L20 30 DCM - 60 26 t Bu L13 30 Benzene 60 88 27 t Bu L13 30 CHCl 3 55 89 28 t Bu L13 30 Toluene 70 89 29 t Bu L13 30 p-xylene 62 91 30 t Bu L13 20 Toluene 57 89 31 t Bu L13 30 p-xylene 86 91 * Entries 1-31 were carried out with 0.2 mmol allyl trifluoromethyl sulfide, 0.24 mmol diazo compound, 10 mol% Cu(CH 3 CN) 4 PF 6, 12 mol% ligand, and 2 ml solvent, the reaction time was 6 h. Unless otherwise noted, the yields were estimated by 19 F NMR (400 MHz) with trifluorotoluene as the internal standard. E.e. values were Determined by HPLC on a chiral stationary phase. Reaction time was 12 h. The reaction of entry 31 was carried out with 0.2 mmol allyl trifluoromethyl sulfide, 0.4 mmol diazo compound, 5 mol% Cu(CH 3 CN) 4 PF 6, 6 mol% ligand, and 2 ml solvent. Isolated yield with preparative thin-layer chromatography. 5.3. General procedure for Cu(I)-catalyzed [2,3]-sigmatropic rearrangement Under a nitrogen atmosphere, Cu(CH 3 CN) 4 PF 6 (3.7 mg, 0.01 mmol, 5 mol%), L13 (6.5 mg, 0.013 mmol, 6 mol%) were added to a dry 10 ml reaction tube, successively. Then the reaction system was stirred at room temperature for 2 h after 2.0 ml p-xylene was added. Then allyl trifluoromethyl sulfide (28 mg, 0.2 mmol, 1.0 equiv.) and aryldiazoacetate (0.4 mmol, 2.0 equiv.) were added to the reaction tube. The reaction tube was then immersed in 30 o C bath. After about 6-10 h, the reaction was stopped when the characteristic color of diazo compound completely disappeared. The solvent was removed with rotary evaporator under reduced pressure to leave a crude mixture, which was purified by preparative thin-layer chromatography to afford the pure product. The corresponding racemic product was prepared with Cu(CH 3 CN) 4 PF 6 in the absence of ligand. 5.4. Mechanistic studies for Cu(I)-catalyzed reaction 5.4.1. Cu(I)/L*-catalyzed reaction with diallyl sulfide 13 9

General procedure: Under a nitrogen atmosphere, Cu(CH 3 CN) 4 PF 6 (3.7 mg, 0.01 mmol, 5 mol%), L * (0.013 mmol, 6 mol% for L13 and L22 or 0.026 mmol, 12 mol% for L6 and L21) were added to a dry 10 ml reaction tube, successively. Then the reaction system was stirred at room temperature for 2 h after 2.0 ml p-xylene was added. Then diallylic sulfide (23 mg, 0.2 mmol, 1.0 equiv.) and aryldiazoacetates (0.4 mmol, 2.0 equiv.) were added to the reaction tube. And the reaction tube was immersed in 30 o C bath. After about 8 h, the reaction was stopped when the color of diazo compounds disappeared. The solvent was removed with rotary evaporators to leave a crude mixture, which was purified by preparation thin-layer chromatography to afford pure product. The corresponding racemic product was prepared with Rh 2 (OAc) 4 as catalyst and dichloromethane as solvent. 5.4.2. Cu(I)/L*-catalyzed reaction with diallyl sulfide 11 10

General procedure: Under a nitrogen atmosphere, Cu(CH 3 CN) 4 PF 6 (3.7 mg, 0.01 mmol, 10 mol%), L (0.013 mmol, 12 mol% for L13 and L22 or 0.026 mmol, 24 mol% for L6 and L21) were added to a dry 10 ml reaction tube, successively. Then the reaction system was stirred at room temperature for 2 h after 2.0 ml p-xylene was added. Then allylic sulfide 11 (22 mg, 0.1 mmol, 1.0 equiv.), aryldiazoacetates 9a (0.2 mmol, 2.0 equiv.) was added to the reaction tube. The reaction tube was then immersed in 30 o C bath. After about 8 h, the reaction was stopped when the color of diazo compounds disappeared. The solvent was removed with rotary evaporators to leave a crude mixture, which was purified by preparation thin-layer chromatography to afford pure product. The d.r. values were determined through 1 H NMR. 6. Characterization data for the products Ethyl 2-phenyl-2-((trifluoromethyl)thio)pent-4-enoate (3a) Yield: 58 mg, 95%, colorless oil; HPLC gave 91% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.48 (petroleum:ethyl acetate = 20:1); [α] 20 D = -55.0 o (c 1.41, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.44-7.42 (m, 2H), 7.38-7.29 (m, 3H), 5.92-5.82 (m, 1H), 5.19 (s, 1H), 5.16 (d, J = 8.3 Hz, 1H), 4.27-4.14 (m, 2H), 3.23 (d, J = 6.9 Hz, 2H), 1.21 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.5, 138.3, 132.0, 129.8 (q, J = 308.8 Hz, 1C), 128.5, 128.3, 126.8, 120.0, 64.8, 62.6, 40.9, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 14 H 15 O 2 F 3 S = 304.0739, found 304.0735; IR (film): 2990, 1732, 1224, 1107, 1024, 757 cm -1. Ethyl 2-(4-tolyl)-2-((trifluoromethyl)thio)pent-4-enoate (3b) Yield: 56 mg, 88%, colorless oil; HPLC gave 89% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, 20 wavelength = 210 nm; R f = 0.50 (petroleum:ethyl acetate = 20:1); [α] D 11

= -59.5 o (c 1.64, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.31 (d, J = 8.2 Hz, 2H), 7.16 (d, J = 8.1 Hz, 2H), 5.91-5.81 (m, 1H), 5.18 (s, 1H), 5.15 (d, J = 6.5 Hz, 1H), 4.26-4.13 (m, 2H), 3.22 (d, J = 6.9 Hz, 2H), 2.34 (s, 3H), 1.21 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.6, 138.1, 135.2, 132.1, 129.8 (q, J = 308.8 Hz), 129.2, 126.7, 119.8, 64.6, 62.5, 40.9, 21.0, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 15 H 17 O 2 F 3 S = 318.0896, found 318.0893; IR (film): 2972, 2901, 1731, 1221, 1108, 929, 758, 655 cm -1. Ethyl 2-(4-fluorophenyl)-2-((trifluoromethyl)thio)pent-4-enoate (3c) Yield: 63 mg, 98%, colorless oil; HPLC gave 91% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, 20 wavelength = 210 nm; R f = 0.49 (petroleum:ethyl acetate = 20:1); [α] D = -61.5 o (c 1.98, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.45-7.41 (m, 2H), 7.07-7.03 (m, 2H), 5.92-5.81 (m, 1H), 5.21-5.16 (m, 2H), 4.27-4.14 (m, 2H), 3.21 (d, J = 6.9 Hz, 2H), 1.21 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.3, 162.3 (d, J = 248.6 Hz, 1C), 134.3 (d, J = 3.5 Hz, 1C), 131.8, 129.6 (q, J = 308.8 Hz, 1C), 128.8 (d, J = 8.3 Hz, 1C), 120.3, 115.5 (d, J = 21.6 Hz, 1C), 64.4, 62.8, 41.0, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F), -113.2-(-113.3) (m, 1F); HRMS (EI, m/z): calcd for [M + ] C 14 H 14 O 2 F 4 S = 322.0645, found 322.0640; IR (film): 2972, 1732, 1511, 1223, 1106, 757 cm -1. Ethyl 2-(4-bromophenyl)-2-((trifluoromethyl)thio)pent-4-enoate (3d) Yield: 58 mg, 76%, colorless oil; HPLC gave 86% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.58 (petroleum:ethyl acetate = 20:1); [α] 20 D = -63.9 o (c 2.20, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.49 (d, J = 8.6 Hz, 2H), 7.32 (d, J = 8.7 Hz, 2H), 5.90-5.80 (m, 1H), 5.21-5.15 (m, 2H), 4.26-4.13 (m, 2H); 3.24-3.14 (m, 2H), 1.21 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.0, 137.6, 131.7, 131.6, 129.6 (q, J = 308.9 Hz, 1C), 128.7, 122.5, 120.4, 64.4, 62.9, 40.8, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.0 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 14 H 14 O 2 BrF 3 S = 381.9844, found 381.9842; IR (film): 2983, 1732, 1221, 1105, 1011, 757 cm -1. Ethyl 2-(4-methoxyphenyl)-2-((trifluoromethyl)thio)pent-4-enoate (3e) Yield: 48 mg, 73%, colorless oil; HPLC gave 79% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.40 (petroleum:ethyl acetate = 20:1); 12

[α] 20 D = -57.4 o (c 1.52, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.38-7.34 (m, 2H), 6.90-6.86 (m, 2H), 5.92-5.82 (m, 1H), 5.19 (s, 1H), 5.17-5.15 (m, 1H), 4.26-4.13 (m, 2H), 3.81 (s, 3H), 3.21 (d, J = 6.9 Hz, 2H), 1.22 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.7, 159.3, 132.2, 130.2, 129.8 (q, J = 308.8 Hz, 1C), 128.2, 119.9, 113.8, 64.6, 62.6, 55.2, 41.0, 13.9; 19 F NMR (CDCl 3, 376 MHz) δ -37.2 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 15 H 17 O 3 F 3 S = 334.0845, found 334.0842; IR (film): 2975, 2900, 1729, 1513, 1256, 1220, 1185, 1107 cm -1. Ethyl 2-([1,1'-biphenyl]-4-yl)-2-((trifluoromethyl)thio)pent-4-enoate (3f) Yield: 49 mg, 64%, colorless oil; HPLC gave 88% e.e., conditions: Daicel chiral column OD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.49 (petroleum:ethyl acetate = 20:1); [α] 20 D = -72.1 o (c 1.75, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.61-7.58 (m, 4H), 7.52-7.49 (m, 2H), 7.45-7.42 (m, 2H), 7.37-7.33 (m, 1H), 5.95-5.84 (m, 1H), 5.21 (s, 1H), 5.18 (d, J = 4.0 Hz, 1H), 4.27-4.16 (m, 2H), 3.27 (d, J = 6.9 Hz, 2H), 1.23 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.4, 141.0, 140.0, 137.2, 131.9, 129.8 (q, J = 308.9 Hz, 1C), 128.8, 127.6, 127.3, 127.0, 127.0, 120.1, 64.6, 62.7, 40.9, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.0 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 20 H 19 O 2 F 3 S = 380.1052, found 380.1050; IR (film): 2983, 1730, 1221, 1106, 759, 697 cm -1. Ethyl 2-(2-fluorophenyl)-2-((trifluoromethyl)thio)pent-4-enoate (3g) Yield: 63 mg, 99%, colorless oil; HPLC gave 75% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.53 (petroleum:ethyl acetate = 20:1); [α] 20 D = -24.8 o (c 2.30, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.49-7.45 (m, 1H), 7.38-7.33 (m, 1H), 7.17 (dt, J = 1.2, 7.7 Hz, 1H), 7.07 (ddd, J = 1.2, 8.2, 11.5 Hz, 1H), 5.90-5.80 (m, 1H), 5.20-5.15 (m, 2H), 4.29-4.17 (m, 2H), 3.22 (ddd, J = 7.1, 14.3, 22.4 Hz, 2H), 1.22 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 169.7, 160.2 (d, J = 7.1 Hz, 1C), 131.1, 130.4 (d, J = 8.9 Hz, 1C), 129.7 (d, J = 308.3 Hz, 1C), 127.9, 126.5 (d, J = 11.3 Hz, 1C), 123.9 (d, J = 3.5 Hz, 1C), 120.4, 115.9 (d, J = 22.1 Hz, 1C), 62.7, 60.5, 41.3, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.2 (s, 3F), -108.9-(-109.0) (m, 1F); HRMS (EI, m/z): calcd for [M + ] C 14 H 14 O 2 F 4 S = 322.0645, found 322.0642; IR (film): 2982, 1741, 1234, 1219, 1106, 757 cm -1 13

Ethyl 2-(2-chlorophenyl)-2-((trifluoromethyl)thio)pent-4-enoate (3h) Yield: 66 mg, 98%, colorless oil; HPLC gave 91% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.49 (petroleum:ethyl acetate = 20:1); [α] 20 D = -60.3 o (c 1.82, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.60-7.56 (m, 1H), 7.44-7.39 (m, 1H), 7.34-7.28 (m, 2H), 5.93-5.83 (m, 1H), 5.21 (s, 1H), 5.18-5.16 (m, 1H), 4.28-4.14 (m, 2H), 3.29 (ddd, J = 7.0, 14.2, 22.4 Hz, 2H), 1.22 (t, J = 7.2 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 169.5, 135.5, 134.4, 131.3, 131.1, 129.7, 129.7 (q, J = 308.7 Hz, 1C), 128.7, 126.5, 120.1, 63.2, 62.7, 42.0, 13.7; 19 F NMR (CDCl 3, 376 MHz) δ -37.2 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 14 H 14 O 2 ClF 3 S = 338.0350, found 338.0347; IR (film): 2981, 1738, 1219, 1105, 1058, 756 cm -1. Ethyl 2-(2-chlorophenyl)-2-((trifluoromethyl)thio)pent-4-enoate (3i) Yield: 84 mg, 98%, colorless oil; HPLC gave 85% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.50 (petroleum:ethyl acetate = 20:1); [α] 20 D = -50.0 o (c 2.34, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 8.00 (dd, J = 1.0 Hz, J = 7.8 Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.39 (t, J = 7.7 Hz, 1H), 7.01 (dt, J = 1.3, 7.7 Hz, 1H), 5.92-5.82 (m, 1H), 5.20 (d, J = 4.5 Hz, 1H), 5.16 (s, 1H), 4.30-4.17 (m, 2H), 3.34 (ddd, J = 7.0, 14.2, 22.3 Hz, 2H), 1.25 (t, J = 7.2 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 169.2, 142.5, 138.9, 131.7, 129.7, 129.6 (q, J = 308.7 Hz, 1C), 129.2, 127.7, 119.9, 99.2, 66.5, 62.9, 42.9, 13.7; 19 F NMR (CDCl 3, 376 MHz) δ -37.2 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 14 H 14 O 2 F 3 IS = 429.9706, found 429.9703; IR (film): 2984, 1736, 1220, 1105, 1016, 756 cm -1. Ethyl 2-(2-tolyl)-2-((trifluoromethyl)thio)pent-4-enoate (3j) Yield: 63 mg, 99%, colorless oil; HPLC gave 90% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.45 (petroleum:ethyl acetate = 20:1); [α] 20 D = -89.4 o (c 2.69, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.45-7.43 (m, 1H), 7.27-7.17 (m, 3H), 6.06-5.96 (m, 1H), 5.23 (s, 1H), 5.20-5.18 (m, 1H), 4.27-4.10 (m, 2H), 3.32 (ddd, J = 7.0, 14.0, 22.2 Hz, 2H), 2.36 (s, 3H), 1.21 (t, J = 7.2 Hz,, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.7, 137.6, 135.7, 132.1, 132.0, 129.7 (q, J = 308.0 Hz, 1C), 128.5, 126.5, 125.7, 119.9, 64.5, 62.6, 42.9, 20.4, 13.9; 19 F NMR (CDCl 3, 376 MHz) δ -37.3 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 15 H 17 O 2 F 3 S = 318.0896, found 318.0895; IR (film): 2986, 1731, 1220, 1105, 1035, 757, 730 cm -1 14

Methyl 3-(1-ethoxy-1-oxo-2-((trifluoromethyl)thio)pent-4-en-2-yl)benzoate (3k) Yield: 32 mg, 44%, colorless oil; HPLC gave 86% e.e., conditions: Daicel chiral column OD-H, hexane: i PrOH = 95:5, 1.0 ml/min, wavelength = 210 nm; R f = 0.28 (petroleum:ethyl acetate = 20:1); [α] 20 D = -63.8 o (c 1.24, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 8.13 (t, J = 1.7 Hz, 1H), 8.02-7.99 (m, 1H), 7.67 (ddd, J = 1.0, 2.1, 8.0 Hz, 1H), 7.46 (t, J = 7.8 Hz, 1H), 5.93-5.83 (m, 1H), 5.22-5.17 (m, 2H), 4.28-4.14 (m, 2H), 3.93 (s, 3H), 3.32-3.22 (m, 2H), 1.21 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.0, 166.4, 139.1, 131.6, 131.5, 130.5, 129.6 (q, J = 309.0 Hz, 1C), 129.5, 128.6, 127.9, 120.4, 64.6, 62.8, 52.2, 40.7, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 16 H 17 O 4 F 3 S = 362.0794, found 362.0794; IR (film): 2971, 2902, 1728, 1281, 1221, 1107 cm -1. Ethyl 2-(naphthalen-2-yl)-2-((trifluoromethyl)thio)pent-4-enoate (3l) Yield: 62 mg, 88%, colorless oil; HPLC gave 84% ee, conditions: Daicel chiral column IC, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.50 (petroleum:ethyl acetate = 20:1); [α] 20 D = -75.2 o (c 0.99, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.88 (d, J = 1.8 Hz, 1H), 7.86-7.80 (m, 3H), 7.55-7.48 (m, 3H), 5.98-5.88 (m, 1H), 5.22 (d, J = 5.2 Hz, 1H), 5.19 (s, 1H), 4.27-4.13 (m, 2H), 3.38 (d, J = 6.9 Hz, 2H), 1.18 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.4, 135.6, 132.8, 132.8, 132.0, 129.8 (q, J = 308.8 Hz, 1C), 128.3, 127.5, 126.7, 126.5, 125.6, 124.9, 120.1, 65.2, 62.7, 40.7, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.0 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 18 H 17 O 2 F 3 S = 354.0896, found 354.0894; IR (film): 2988, 1730, 1221, 1106, 1024, 756 cm -1. Ethyl 2-(thiophen-3-yl)-2-((trifluoromethyl)thio)pent-4-enoate (3m) Yield: 52 mg, 84%, colorless oil; HPLC gave 92% e.e., conditions: Daicel chiral column IC, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.54 (petroleum:ethyl acetate = 20:1); [α] 20 D = -49.5 o (c 2.06, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.35 (dd, J = 1.4, 3.0 Hz, 1H), 7.30 (dd, J = 3.0, 5.1 Hz, 1H), 7.13 (dd, J = 1.4, 5.1 Hz, 1H), 5.87-5.77 (m, 1H), 5.19-5.15 (m, 2H), 4.28-4.17 (m, 2H), 3.21 (d, J = 6.9 Hz, 2H), 1.25 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 169.8, 138.4, 131.9, 129.6 (q, J = 309.1 Hz, 1C), 126.9, 125.9, 123.3, 120.0, 62.7, 61.2, 41.6, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.6 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 12 H 13 O 2 F 3 S 2 = 310.0304, found 310.0302; IR (film): 2987, 1732, 1217, 1106, 1025, 781 cm -1. 15

Methyl (E)-2-styryl-2-((trifluoromethyl)thio)pent-4-enoate (5a) Yield: 63 mg, 99%, colorless oil; HPLC gave 98% e.e., conditions: Daicel chiral column OJ-H + OJ, hexane: i PrOH = 100:0, 0.8 ml/min, wavelength = 210 nm; R f = 0.51 (petroleum:ethyl acetate = 20:1); [α] 20 D = -13.6 o (c 2.58, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.41-7.39 (m, 2H), 7.36-7.32 (m, 2H), 7.30-7.26 (m, 1H), 6.78 (d, J = 16.2 Hz, 1H), 6.47 (d, J = 16.2 Hz, 1H), 5.87-5.77 (m, 1H), 5.23-5.21 (m, 1H), 5.19 (s, 1H), 3.81 (s, 3H), 3.00 (d, J = 6.9 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 170.4, 135.8, 133.5, 131.4, 129.6 (q, J = 309.3 Hz, 1C), 128.6, 128.4, 126.7, 125.8, 120.2, 60.2, 53.3, 41.3; 19 F NMR (CDCl 3, 376 MHz) δ -36.9 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 15 H 15 O 2 F 3 S = 316.0739, found 316.0740; IR (film): 2953, 1740, 1224, 1106, 748, 692 cm -1. Methyl (E)-2-(4-methylstyryl)-2-((trifluoromethyl)thio)pent-4-enoate (5b) Yield: 65 mg, 99%, colorless oil; HPLC gave 95% e.e., conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.49 (petroleum:ethyl acetate = 20:1); [α] 20 D = -25.2 o (c 2.22, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.29 (d, J = 8.1 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.74 (d, J = 16.2 Hz, 1H), 6.41 (d, J = 16.2 Hz, 1H), 5.87-5.77 (m, 1H), 5.23-5.20 (m, 1H), 5.18 (s, 1H), 3.80 (s, 3H), 3.00 (d, J = 6.9 Hz, 2H), 2.34 (s, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.5, 138.4, 133.4, 133.0, 131.6, 129.6 (q, J = 309.4 Hz, 1C), 129.3, 126.6, 124.7, 120.1, 60.3, 53.2, 41.3, 21.1; 19 F NMR (CDCl 3, 376 MHz) δ -36.9 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 16 H 17 O 2 F 3 S = 330.0896, found 330.0896; IR (film): 2972, 2900, 1740, 1224, 1105, 969, 807 cm -1. Methyl (E)-2-(4-methylstyryl)-2-((trifluoromethyl)thio)pent-4-enoate (5c) Yield: 51 mg, 74%, colorless oil; HPLC gave 76% e.e., conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.32 (petroleum:ethyl acetate = 20:1); [α] 20 D = -15.6 o (c 1.76, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.35-7.32 (m, 2H), 6.89-6.85 (m, 2H), 6.71 (d, J = 16.2 Hz, 1H), 6.31 (d, J = 16.2 Hz, 1H), 5.88-5.78 (m, 1H), 5.23-5.20 (m, 1H), 5.18 (s, 1H), 3.81 (s, 6H), 3.00 (d, J = 6.9 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 170.6, 159.9, 133.0, 131.7, 129.69 (q, J = 309.4 Hz, 1C), 128.6, 128.0, 123.4, 120.1, 114.1, 60.4, 55.3, 53.3, 41.3; 19 F NMR (CDCl 3, 376 MHz) δ -37.0 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 16 H 17 O 3 F 3 S = 346.0845, found 346.0845; IR (film): 2959, 1739, 1513, 1254, 16

1106, 1034 cm -1. Methyl (E)-2-(4-fluorostyryl)-2-((trifluoromethyl)thio)pent-4-enoate (5d) Yield: 66 mg, 98%, colorless oil; HPLC gave 98% ee, conditions: Daicel chiral column OJ-H + OJ, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.44 (petroleum:ethyl acetate = 20:1); [α] 20 D = -11.7 o (c 1,58, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.39-7.35 (m, 2H), 7.06-7.00 (m, 2H), 6.74 (d, J = 16.2 Hz, 1H), 6.39 (d, J = 16.2 Hz, 1H), 5.86-5.76 (m, 1H), 5.23-5.22 (m, 1H), 5.19 (s, 1H), 3.82 (s, 3H), 2.98 (d, J = 6.8 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 170.5, 162.8 (d, J = 248.1, 1C), 132.2, 132.1 (d, J = 3.5 Hz, 1C), 131.4, 129.6 (q, J = 309.4 Hz, 1C), 128.4 (d, J = 8.1 Hz, 1C), 125.7 (d, J = 1.7 Hz, 1C), 120.3, 115.6 (d, J = 21.9 Hz, 1C), 60.1, 53.3, 41.4; 19 F NMR (CDCl 3, 376 MHz) δ -36.9 (s, 3F), -113.0-(-113.0) (m, 1F); HRMS (EI, m/z): calcd for [M + ] C 15 H 14 O 2 F 4 S = 334.0645, found 334.0644; IR (film): 2987, 1740, 1510, 1230, 1105, 819 cm -1 Methyl (E)-2-(4-chlorostyryl)-2-((trifluoromethyl)thio)pent-4-enoate (5e) Yield: 69 mg, 99%, colorless oil; HPLC gave 98% e.e., conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.44 (petroleum:ethyl acetate = 20:1); [α] 20 D = -13.0 o (c 3.20, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.34-7.29 (m, 4H), 6.73 (d, J = 16.2 Hz, 1H), 6.46 (d, J = 15.6 Hz, 1H), 5.85-5.75 (m, 1H), 5.23-5.22 (m, 1H), 5.19 (s, 1H), 3.81 (s, 3H), 3.03-2.93 (m, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 170.3, 134.3, 134.1, 132.2, 131.2, 129.6 (q, J = 309.5 Hz, 1C), 128.8, 127.9, 126.6, 120.3, 60.0, 53.3, 41.3; 19 F NMR (CDCl 3, 376 MHz) δ -37.0 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 15 H 14 O 2 ClF 3 S = 350.0350, found 350.0349; IR (film): 2956, 1740, 1492, 1224, 1104, 959, 812 cm -1. Methyl (E)-2-(4-chlorostyryl)-2-((trifluoromethyl)thio)pent-4-enoate (5f) Yield: 77 mg, 98%, colorless oil; HPLC gave 98% e.e., conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.49 (petroleum:ethyl acetate = 20:1); [α] 20 D = -12.4 o (c 3.24, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.48-7.44 (m, 2H), 7.28-7.25 (m, 2H), 6.72 (d, J = 16.2 Hz, 1H), 6.48 (d, J = 16.2 Hz, 1H), 5.85-5.74 (m, 1H), 5.23-5.22 (m, 1H), 5.19 (s, 1H), 3.81 (s, 3H), 2.98 (d, J = 6.8 Hz, 2H); 13 C NMR (CDCl 3, 100 17

MHz) δ 170.3, 134.7, 132.2, 131.8, 131.2, 129.6 (q, J = 309.5 Hz, 1C), 128.2, 126.7, 122.3, 120.3, 60.0, 53.3, 41.3; 19 F NMR (CDCl 3, 376 MHz) δ -36.9 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 15 H 14 O 2 BrF 3 S = 393.9844, found 393.9844; IR (film): 2953, 1739, 1489, 1224, 1105, 810 cm -1. Methyl (E)-2-(4-iodostyryl)-2-((trifluoromethyl)thio)pent-4-enoate (5g) Yield: 74 mg, 84%, colorless oil; HPLC gave 96% e.e., conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.48 (petroleum:ethyl acetate = 20:1); [α] 20 D = -12.4 o (c 3.26, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.68-7.65 (m, 2H), 7.14-7.12 (m, 2H), 6.70 (d, J = 16.2 Hz, 1H), 6.49 (d, J = 16.2 Hz, 1H), 5.84-7.74 (m, 1H), 5.25-5.21 (m, 1H), 5.18 (d, J = 0.8 Hz,1H), 3.81 (s, 3H), 2.97 (d, J = 6.8 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 170.3, 137.8, 135.4, 132.4, 131.3, 129.6 (q, J = 309.5 Hz, 1C), 128.4, 126.9, 120.4, 94.0, 60.1, 53.4, 41.3; 19 F NMR (CDCl 3, 376 MHz) δ -36.8 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 15 H 14 O 2 F 3 IS = 441.9706, found 441.9710; IR (film): 2987, 1739, 1224, 1105, 1005, 808 cm -1. Methyl (E)-2-(4-(trifluoromethyl)styryl)-2-((trifluoromethyl)thio)pent-4-enoate (5h) Yield: 74 mg, 94%, colorless oil; HPLC gave 96% e.e., conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.52 (petroleum:ethyl acetate = 20:1); [α] 20 D = -8.89 o (c 3.16, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.59 (d, J = 8.2 Hz, 2H), 7.50 (d, J = 8.2 Hz, 2H), 6.83 (d, J = 16.3 Hz, 1H), 6.60 (d, J = 16.2 Hz, 1H), 5.85-5.75 (m, 1H), 5.24-5.23 (m, 1H), 5.20 (d, J = 0.7 Hz, 1H), 3.83 (s, 3H), 3.00 (d, J = 6.7 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 170.2, 139.4, 132.0, 131.1, 130.2, 129.6 (q, J = 309.4 Hz, 1C), 128.9, 127.0, 125.7 (q, J = 3.7 Hz, 1C), 124.0 (q, J = 271.9 Hz, 1C), 120.6, 60.0, 53.5, 41.4; 19 F NMR (CDCl 3, 376 MHz) δ -36.9 (s, 3F), -62.8 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 16 H 14 O 2 F 6 S = 384.0613, found 384.0614; IR (film): 2960, 1741, 1325, 1225, 1107, 1068 cm -1. 18

Methyl (E)-4-(3-(methoxycarbonyl)-3-((trifluoromethyl)thio)hexa-1,5-dien-1-yl) benzoate (5i) Yield: 65 mg, 87%, colorless oil; HPLC gave 93% e.e., conditions: Daicel chiral column OJ-H+OJ, hexane: i PrOH = 96:4, 1.0 ml/min, wavelength = 210 nm; R f = 0.23 (petroleum:ethyl acetate = 20:1); [α] 20 D = -13.6 o (c 2.65, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 8.01 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 8.3 Hz, 2H), 6.82 (d, J = 16.3 Hz, 1H), 6.61 (d, J = 16.2 Hz, 1H), 5.86-5.75 (m, 1H), 5.24-5.23 (m, 1H), 5.20 (s, 1H), 3.92 (s, 3H), 3.83 (s, 3H), 2.99 (d, J = 6.8 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 170.2, 166.6, 140.2, 132.4, 131.1, 130.0, 129.8, 129.6 (q, J = 309.3 Hz, 1C), 128.6, 126.6, 120.5, 60.1, 53.4, 52.1, 41.3; 19 F NMR (CDCl 3, 376 MHz) δ -36.9 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 17 H 17 O 4 F 3 S = 374.0794, found 374.0796; IR (film): 2989, 2907, 1723, 1281, 1106, 763 cm -1. Methyl (E)-2-(2-fluorostyryl)-2-((trifluoromethyl)thio)pent-4-enoate (5j) Yield: 63 mg, 94%, colorless oil; HPLC gave 93% e.e., conditions: Daicel chiral column OD-H+OD-H, hexane: i PrOH = 100:0, 0.6 ml/min, wavelength = 210 nm; R f = 0.49 (petroleum:ethyl acetate = 20:1); [α] 20 D = -13.4 o (c 2.36, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.49-7.44 (m, 1H), 7.29-7.23 (m, 1H), 7.14-7.10 (m, 1H), 7.08-7.03 (m, 1H), 6.94 (d, J = 16.4 Hz, 1H), 6.58 (d, J = 16.4 Hz, 1H), 5.87-5.76 (m, 1H), 5.24-5.22 (m, 1H), 5.19 (s, 1H), 3.82 (s, 3H), 3.00 (d, J = 7.0 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 170.4, 160.4 (d, J = 250.4 Hz, 1C), 131.3, 129.8 (d, J = 8.4 Hz, 1C), 129.6 (q, J = 309.2 Hz, 1C), 128.4 (d, J = 4.8 Hz, 1C), 127.5 (d, J = 3.2 Hz, 1C), 126.0 (d, J = 3.8 Hz, 1C), 124.3 (d, J = 3.5 Hz, 1C), 123.8 (d, J = 12.2 Hz, 1C), 120.4, 115.8 (d, J = 22.0 Hz, 1C), 60.4, 53.4, 41.3; 19 F NMR (CDCl 3, 376 MHz) δ -36.8 (s, 3F), -117.4-(-117.5) (m, 1F); HRMS (EI, m/z): calcd for [M + ] C 15 H 14 O 2 F 4 S = 334.0645, found 334.0646; IR (film): 2956, 1740, 1488, 1232, 1105, 756 cm -1. Methyl (E)-2-(2-methylstyryl)-2-((trifluoromethyl)thio)pent-4-enoate (5k) Yield: 50 mg, 76%, colorless oil; HPLC gave 86% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.44 (petroleum:ethyl acetate = 20:1); [α] 20 D = -1.86 o (c 1.62, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.41-7.39 (m, 1H), 7.22-7.14 (m, 3H), 7.02 (d, J = 16.1 Hz, 1H), 6.32 (d, J = 16.1 Hz, 1H), 5.88-5.76 (m, 1H), 5.23 (d, J = 5.8 Hz, 1H), 5.20 (s, 1H), 3.81 (s, 19

3H), 3.06-2.96 (m, 2H), 2.34 (s, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.5, 135.9, 135.2, 131.8, 131.5, 130.2, 129.6 (q, J = 309.5 Hz, 1H), 128.2, 127.2, 126.2, 125.9, 120.1, 60.3, 53.2, 41.5, 19.6; 19 F NMR (CDCl 3, 376 MHz) δ -36.9 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 16 H 17 O 2 F 3 S = 330.0896, found 330.0897; IR (film): 2974, 2901, 1741, 1222, 1107, 751 cm -1. Methyl (E)-2-(2-(naphthalen-2-yl)vinyl)-2-((trifluoromethyl)thio)pent-4-enoate (5l) Yield: 51 mg, 76%, colorless oil; HPLC gave 93% e.e., conditions: Daicel chiral column OJ-H+OJ, hexane: i PrOH = 94:6, 0.5 ml/min, wavelength = 210 nm; R f = 0.46 (petroleum:ethyl acetate = 20:1); [α] 20 D = -11.9 o (c 2.42, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.83 (m, 4H), 7.60-7.58 (m, 1H), 7.49-7.43 (m, 2H), 6.94 (d, J = 16.2 Hz, 1H), 6.60 (d, J = 16.2 Hz, 1H), 5.90-5.80 (m, 1H), 5.26-5.20 (m, 2H), 3.83 (s, 3H), 3.04 (d, J = 7.0 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 170.5, 133.6, 133.4, 133.3, 133.2, 131.5, 129.6 (q, J = 309.6 Hz, 1C), 128.4, 128.0, 127.6, 127.2, 126.4, 126.3, 126.1, 123.3, 120.2, 60.3, 53.3, 41.3; 19 F NMR (CDCl 3, 376 MHz) δ -36.9 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C19H17O2F3S = 366.0896, found 366.0897; IR (film): 2989, 1740, 1224, 1105, 963, 813, 746 cm -1. Methyl (3E, 5E)-2-allyl-6-phenyl-2-((trifluoromethyl)thio)hexa-3,5-dienoate (5m) Yield: 61 mg, 89%, colorless oil; HPLC gave 94% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.51 (petroleum:ethyl acetate = 20:1); [α] 20 D = -16.4 o (c 2.96, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.41-7.39 (m, 2H), 7.34-7.30 (m, 2H), 7.26-7.22 (m, 1H), 6.78 (dd, J = 10.3 Hz, J = 15.6 Hz, 1H), 6.65-6.54 (m, 2H), 6.06 (d, J = 15.4 Hz, 1H), 5.84-5.74 (m, 1H), 5.22-5.17 (m, 2H), 3.80 (s, 3H), 2.99-2.89 (m, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 170.4, 136.6, 134.8, 134.0, 131.4, 129.6 (q, J = 309.4 Hz, 1C), 129.0, 128.6, 128.0, 127.4, 126.5, 120.1, 60.1, 53.2, 41.2; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 17 H 17 O 2 F 3 S = 342.0896, found 342.0897; IR (film): 2956, 1739, 1221, 1105, 989, 691 cm -1. Methyl (E)-2-allyl-2-((trifluoromethyl)thio)pent-3-enoate (5n) Yield: 42 mg, 82%, colorless oil; HPLC gave 93% e.e., conditions: Daicel chiral column IC+IC, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.47 (petroleum:ethyl acetate = 20:1); [α] 20 D = -8,86 o (c 0.92, 20

CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 5.94-5.83 (m, 1H), 5.81-5.71 (m, 2H),5.18 (s, 1H), 5.15-5.13 (m, 1H), 3.78 (s, 3H), 2.93-2.83 (m, 2H), 1.77 (dd, J = 1.5 Hz, J = 6.5 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 170.8, 131.8, 130.4, 129.7 (q, J = 309.3 Hz, 1C), 127.4, 119.7, 60.0, 53.1, 41.1, 18.1; 19 F NMR (CDCl 3, 376 MHz) δ -37.2 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 10 H 13 O 2 F 3 S = 254.0583, found 254.0583; IR (film): 2955, 1741, 1223, 1105, 967, 925 cm -1. Ethyl 2-phenyl-2-((trifluoromethyl)thio)penta-3,4-dienoate (7a) Yield: 39 mg, 65%, colorless oil; HPLC gave 90% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.35 (petroleum:ethyl acetate = 30:1); [α] 20 D = -37.4 o (c 0.58, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.52-7.49 (m, 2H), 7.39-7.31 (m, 3H), 6.03 (t, J = 6.6 Hz, 1H), 4.98 (d, J = 6.2 Hz, 2H), 4.26 (t, J = 10.7 Hz, 2H), 1.24 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.6, 169.5, 137.0, 129.4 (q, J = 309.8 Hz, 1C), 128.6, 128.4, 127.5, 93.2, 80.0, 63.5, 62.9, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 14 H 13 F 3 O 2 S = 302.0583, found 302.0581; IR (film): 1733, 1234, 1104, 855,726, 696 cm -1. Ethyl 2-(4-tolyl)-2-((trifluoromethyl)thio)penta-3,4-dienoate (7b) Yield: 34 mg, 55%, colorless oil; HPLC gave 87% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, 20 wavelength = 210 nm; R f = 0.36 (petroleum:ethyl acetate = 30:1); [α] D = -35.0 o (c 1.28, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.38 (d, J = 8.3 Hz, 2H), 7.16 (d, J = 8.1 Hz, 2H), 6.01 (t, J = 6.6 Hz, 1H), 4.98 (d, J = 6.7 Hz, 2H), 4.25 (dq, J = 1.0, 7.1 Hz, 2H), 2.34 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.6, 169.6, 138.5, 134.0, 129.4 (q, J = 310.0 Hz, 1C), 129.1, 127.4, 93.3, 79.9, 63.3, 62.9, 21.0, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.2 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 15 H 15 O 2 F 3 S = 316.0739, found 316.0740; IR (film): 1733, 1234, 1104, 1023, 855 cm -1. Ethyl 2-(4-fluorophenyl)-2-((trifluoromethyl)thio)penta-3,4-dienoate (7c) Yield: 48 mg, 74%, colorless oil; HPLC gave 92% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, 20 wavelength = 210 nm; R f = 0.35 (petroleum:ethyl acetate = 30:1); [α] D = -40.5 o (c 1.00, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.52-7.49 (m, 2H), 7.08-7.02 (m, 2H), 5.99 (t, J = 6.6 Hz, 1H), 4.99 (d, J = 6.7 Hz, 2H), 4.25 (q, J = 7.2 Hz, 2H), 1.25 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.7, 169.3, 162.6 (d, J = 249.0 21

Hz, 1C), 133.0 (d, J = 3.2 Hz, 1C), 129.7 (d, J = 8.4 Hz, 1C), 129.3 (q, J = 309.7 Hz, 1C), 115.4 (d, J = 21.8 Hz, 1C), 93.2, 80.2, 63.1, 63.0, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F), -113.0-(-113.0) (m, 1F); HRMS (EI, m/z): calcd for [M + ] C 14 H 12 O 2 F 4 S = 320.0489, found 320.0491; IR (film): 1735, 1508, 1235, 1103, 853, 839 cm -1. Ethyl 2-(4-methoxyphenyl)-2-((trifluoromethyl)thio)penta-3,4-dienoate (7d) Yield: 40 mg, 61%, colorless oil; HPLC gave 67% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.23 (petroleum:ethyl acetate = 30:1); [α] 20 D = -29.4 o (c 1.43, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.45-7.41 (m, 2H), 6.90-6.86 (m, 2H), 6.01 (t, J = 6.6 Hz, 1H), 4.99 (d, J = 6.7 Hz, 2H), 4.25 (q, J = 7.1 Hz, 2H), 3.81 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.6, 169.6, 159.6, 129.4 (q, J = 310.0 Hz, 1C), 128.9, 128.8, 113.8, 93.4, 79.9, 63.1, 62.9, 55.2, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.3 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 15 H 15 O 3 F 3 S = 332.0688, found 332.0694; IR (film): 1731, 1510, 1255, 1236, 1102, 1034, 854 cm -1. Ethyl 2-(2-chlorophenyl)-2-((trifluoromethyl)thio)penta-3,4-dienoate (7e) Yield: 22 mg, 33%, colorless oil; HPLC gave 81% e.e., conditions: Daicel chiral column OJ-H+OJ, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.46 (petroleum:ethyl acetate = 30:1); [α] 20 D = -33.3 o (c 0.68, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.78-7.76 (m, 1H), 7.41-7.38 (m, 1H), 7.34-7.29 (m, 2H), 6.06 (t, J = 6.6 Hz, 1H), 4.95 (d, J = 6.6 Hz, 2H), 4.32-4.19 (m, 2H), 1.24 (t, J = 7.2 Hz,3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.6, 168.6, 135.0, 134.2, 130.7, 130.3, 129.8, 129.1 (q, J = 309.8 Hz, 1C), 126.4, 92.9, 80.4, 63.1, 62.6, 13.6; 19 F NMR (CDCl 3, 376 MHz) δ -38.0 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 14 H 12 O 2 ClF 3 S = 336.0193, found 336.0204; IR (film): 1741, 1231, 1104, 857, 756 cm -1. Ethyl 2-(thiophen-2-yl)-2-((trifluoromethyl)thio)penta-3,4-dienoate (7f) Yield: 40 mg, 65%, colorless oil; HPLC gave 84% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.46 (petroleum:ethyl acetate = 30:1); [α] 20 D = -34.7 o (c 1.42, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.42 (dd, J = 1.4, 3.0 Hz, 1H), 7.30 (dd, J = 3.0, 5.1 Hz, 1H), 7.14 (dd, J =1.4, 5.1 Hz, 1H), 6.02 (t, J = 6.6 Hz, 1H), 4.99 (dd, J = 1.9, 6.7 Hz, 2H), 4.27 (q, J = 7.1 Hz, 2H), 1.28 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.5, 169.0, 137.2, 129.3 (q, J = 310.2, 1C), 127.1, 126.0, 124.6, 93.3, 80.2, 63.0, 22

59.6, 13.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.7(s, 3F); HRMS (EI, m/z): calcd for [M + ] C 12 H 11 O 2 F 3 S 2 = 308.0147, found 308.0154; IR (film): 1734, 1242, 1220, 1105, 856 cm -1. Methyl (E)-2-styryl-2-((trifluoromethyl)thio) penta-3,4-dienoate (7g) Yield: 49 mg, 74%, colorless oil; HPLC gave 90% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.46 (petroleum:ethyl acetate = 30:1); [α] 20 D = -25.7 o (c 2.15, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.42-7.40 (m, 2H), 7.36-7.26 (m, 3H), 6.83 (d, J = 16.0 Hz, 1H), 6.54 (d, J = 16.0 Hz, 1H), 5.75 (t, J = 6.6 Hz, 1H), 5.10 (d, J = 6.6 Hz, 2H), 3.83 (s, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.6, 169.7, 135.7, 134.5, 129.5 (q, J = 309.9 Hz, 1C), 128.7, 128.5, 126.9, 125.2, 91.8, 80.5, 59.5, 53.7; 19 F NMR (CDCl 3, 376 MHz) δ -37.2 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 15 H 13 O 2 F 3 S = 314.0583, found 314.0591; IR (film): 1741, 1238, 1105, 755, 692 cm -1. Methyl (E)-2-(p-fluorostyryl)-2-((trifluoromethyl)thio)penta-3,4-dienoate (7h) Yield: 45 mg, 68%, colorless oil; HPLC gave 86% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.31 (petroleum:ethyl acetate = 30:1); [α] 20 D = -20.6 o (c 0.98, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.40-7.36 (m, 2H), 7.05-7.01 (m, 2H), 6.79 (d, J = 16.0 Hz, 1H), 6.46 (d, J = 16.0 Hz, 1H), 5.73 (t, J = 6.6 Hz,, 1H), 5.10 (d, J = 6.6 Hz, 2H), 3.84 (s, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.6, 169.7, 162.9 (d, J = 248.6 Hz, 1C), 133.3, 131.9 (d, J = 3.2 Hz, 1C), 129.4 (q, J = 309.9 Hz, 1C), 128.5 (d, J = 8.2 Hz, 1C), 125.0 (d, J = 1.1 Hz, 1C), 115.7 (d, J = 21.9 Hz, 1C), 91.8, 80.6, 59.4, 53.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.2(s, 3F), -112.8-(-112.8) (m, 1F); HRMS (EI, m/z): calcd for [M + ] C 15 H 12 O 2 F 4 S = 332.0489, found 332.0501; IR (film): 1741, 1510, 1234, 1159, 1105, 855, 819 cm -1. Methyl (E)-2-(4-bromostyryl)-2-((trifluoromethyl)thio)penta-3,4-dienoate (7i) Yield: 42 mg, 54%, colorless oil; HPLC gave 85% e.e., conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.30 (petroleum:ethyl acetate = 30:1); [α] 20 D = -17.8 o (c 1.95, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.48-7.45 (m, 2H), 7.29-7.26 (m, 2H), 6.77 (d, J = 16.0 Hz, 1H), 6.53 (d, J = 15.6 Hz, 1H), 5.72 (t, J = 6.6 Hz, 1H), 5.10 (d, J = 6.6 Hz, 2H), 3.84 (s, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.6, 169.5, 134.6, 133.2, 131.8, 129.4 (q, J = 310.1 Hz, 1C), 128.3, 126.0, 122.4, 91.6, 80.6, 59.3, 53.7; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F); HRMS (EI, m/z): 23

calcd for [M + ] C 15 H 12 O 2 BrF 3 S = 391.9688, found 391.9703; IR (film): 1741, 1239, 1105, 1010, 854, 810 cm -1. Methyl (E)-2-(4-(trifluoromethyl)styryl)-2-((trifluoromethyl)thio)penta-3,4-dienoate (7j) Yield: 65 mg, 85%, colorless oil; HPLC gave 91% e.e., conditions: Daicel chiral column AD-H+AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.27 (petroleum:ethyl acetate = 30:1); [α] 20 D = -16.9 o (c 2.86, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.60 (d, J = 8.3 Hz, 2H), 7.51 (d, J = 8.3 Hz, 2H), 6.87 (d, J = 16.0 Hz, 1H), 6.66 (d, J = 16.0 Hz, 1H), 5.73 (t, J = 6.6 Hz, 1H), 5.12 (d, J = 6.6 Hz, 2H), 3.85 (s, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.7, 169.5, 139.2, 132.9, 130.4 (q, J = 32.7 Hz, 1C), 129.4 (q, J = 309.9 Hz, 1C), 128.1, 127.1, 125.6 (q, J = 3.8 Hz, 1C), 124.0 (q, J = 272, 1C), 91.5, 80.7, 59.2, 53.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F), -62.7 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 16 H 12 O 2 F 6 S = 382.0457, found 382.0470; IR (film): 1742, 1325, 1241, 1106, 1067 cm -1 Methyl (E)-4-(3-(methoxycarbonyl)-3-((trifluoromethyl)thio)hexa-1,4,5-trien-1-yl)benzoate (7k) Yield: 44 mg, 60%, colorless oil; HPLC gave 85% e.e., conditions: Daicel chiral column OJ-H+OJ, hexane: i PrOH = 90:10, 0.8 ml/min, wavelength = 210 nm; R f = 0.39 (petroleum:ethyl acetate = 10:1); [α] 20 D = -17.2 o (c 1.94, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 8.01 (d, J = 8.3 Hz, 2H), 7.47 (d, J = 8.3 Hz, 2H), 6.87 (d, J = 16.0 Hz, 1H), 6.66 (d, J = 16.0 Hz, 1H), 5.73 (t, J = 6.6 Hz, 1H), 5.11 (d, J = 6.6 Hz, 2H), 3.92 (s, 3H), 3.85 (s, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.6, 169.4, 166.6, 140.1, 133.3, 129.9, 129.8, 129.4 (q, J = 310.1 Hz, 1C), 127.8, 126.7, 91.5, 80.7, 59.2, 53.7, 52.1; 19 F NMR (CDCl 3, 376 MHz) δ -37.2 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 17 H 15 O 4 F 3 S = 372.0638, found 372.0656; IR (film): 1722, 1435, 1282, 1240, 1105 cm -1. Methyl (E)-2-(o-fluorostyryl)-2-((trifluoromethyl)thio)penta-3,4-dienoate (7l) Yield: 33 mg, 50%, colorless oil; HPLC gave 70% e.e., conditions: Daicel chiral column OD-H+OD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.31 (petroleum:ethyl acetate = 30:1); [α] 20 D = -17.9 o (c 1.46, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.42-7.37 (m, 1H), 7.22-7.16 (m, 1H), 7.07-7.03 (m, 1H), 7.00-6.95 (m, 1H), 6.91 (d, J = 16.1 Hz, 1H), 6.57 (d, J = 16.1 Hz, 1H), 5.67 (t, J = 6.6 Hz, 1H), 5.03 (d, J = 6.6 Hz, 2H), 3.77 (s, 24

3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.7, 169.6, 160.4 (d, J = 250.5 Hz, 1C), 129.9 (d, J = 8.4 Hz, 1H), 129.4 (q, J = 310.1 Hz, 1C), 127.7 (d, J = 3.2 Hz, 1C), 127.6 (d, J = 5.1 Hz, 1C), 127.0 (d, J = 3.7 Hz, 1C), 124.2 (d, J = 3.6 Hz, 1C), 123.6 (d, J = 12.2 Hz, 1C), 115.8 (d, J = 22.0 Hz, 1C), 91.5, 80.6, 59.6, 53.8; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F), -117.0-(-117.1) (m, 1F); HRMS (EI, m/z): calcd for [M + ] C 15 H 12 O 2 F 4 S = 332.0489, found 332.0501; IR (film): 1739, 1238, 1105, 858, 814, 755 cm -1. Methyl (E)-2-(prop-1-en-1-yl)-2-((trifluoromethyl)thio)penta-3,4-dienoate (7m) Yield: 26 mg, 51%, colorless oil; HPLC gave 90% e.e., conditions: Daicel chiral column OD-H+OD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.42 (petroleum:ethyl acetate = 30:1); [α] 20 D = -27.5 o (c 0.66, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 6.00-5.91 (m, 1H), 5.81 (d, J = 15.5 Hz, 1H), 5.66 (t, J = 6.6 Hz, 1H), 5.04 (d, J = 6.7 Hz, 2H), 3.81 (s, 3H), 1.78 (dd, J = 1.5, 6.5 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 208.5, 170.0, 131.6, 129.5 (q, J= 309.7 Hz, 1C), 126.9, 92.1, 80.1, 59.2, 53.5,17.9; 19 F NMR (CDCl 3, 376 MHz) δ -37.5 (s, 3F); HRMS (EI, m/z): calcd for [M + ] C 10 H 11 O 2 F 3 S = 252.0426, found 252.0437; IR (film): 1741, 1238, 1104, 964, 854 cm -1. 2-([1,1'-biphenyl]-4-yl)-2-((trifluoromethyl)thio)pent-4-en-1-yl 4-nitrobenzoate (8) white solid; HPLC gave 88% e.e., conditions: Daicel chiral column OD-H+OD-H, hexane: i PrOH = 95:5, 0.6 ml/min, wavelength = 210 nm; R f = 0.40 (petroleum:ethyl acetate = 5:1); [α] 20 D = +9.56 o (c 0.56, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 8.30 (d, J = 8.8Hz, 2H), 8.20 (d, J = 8.8 Hz, 2H), 7.66-7.60 (m, 6H), 7.7.47-7.43 (m, 2H), 7.39-7.35 (m, 1H), 5.68-5.58 (m, 1H), 5.17-5.12 (m, 2H), 5.09-5.00 (m, 2H), 3.13-3.00 (m, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 163.9, 150.7, 141.0, 139.8, 137.2, 134.8, 130.8, 129.8 (q, J = 309.2 Hz, 1C), 128.8, 127.7, 127.4, 127.2, 126.9, 123.7, 120.5, 67.4, 57.9, 42.7; 19 F NMR (CDCl 3, 376 MHz) δ -35.5 (s, 3F); IR (film): 2957, 2925, 2853, 1734, 1529, 1273, 1122, 1103, 758 cm -1. tert-butyl 2-phenyl-2-((trifluoromethyl)thio)pent-4-enoate (10a) Yield: 57 mg, 86%, colourless oil; HPLC gave 90% e.e., conditions: Daicel chiral column IC, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.57 (petroleum:ethyl acetate = 50:1); [α] 20 D = +67.0 o (c 1.62, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.46-7.43 (m, 2H), 7.37-7.33 (m, 2H), 7.31-7.27 (m, 1H), 5.98-5.88 (m, 1H), 5.23-5.18 (m, 2H), 3.24-3.16 (m, 2H), 1.39 (s, 25

9H); 13 C NMR (CDCl 3, 100 MHz) δ 169.2, 139.1, 132.2, 129.9 (q, J = 308.7 Hz, 1C), 128.3, 128.0, 126.7, 119.8, 83.7, 65.5, 40.4, 27.6; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F); HRMS (ESI, m/z): calcd for C 16 H 19 F 3 NaO 2 S [(M+Na) + ] 355.0950, found 355.0947; IR (film): 2980, 1724, 1370, 1148, 1104, 838 cm -1. tert-butyl 2-(4-fluorophenyl)-2-((trifluoromethyl)thio)pent-4-enoate (10b) Yield: 64 mg, 91%,colourless oil; HPLC gave 90% e.e., conditions: Daicel chiral column AD-H+OJ-H, hexane: i PrOH = 100:0, 0.5 ml/min, 20 wavelength = 210 nm; R f = 0.57 (petroleum:ethyl acetate = 50:1); [α] D = +94 o (c 1.75, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.46-7.42 (m, 2H), 7.07-7.02 (m, 2H), 5.98-5.87 (m, 1H), 5.24-5.19 (m, 2H), 3.24-3.13 (m, 2H), 1.39 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 169.0, 162.2 (d, J = 248.1 Hz,, 1C), 135.2 (d, J = 3.4 Hz, 1C), 132.0, 129.8 (q, J = 308.8 Hz, 1C), 128.7 (d, J = 8.3 Hz, 1C), 120.1, 115.3 (d, J = 21.8 Hz, 1C), 84.0, 65.1, 40.6, 27.6; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F), -113.6- (-113.7) (m, 1F); HRMS (ESI, m/z): calcd for C 16 H 18 F 4 NaO 2 S [(M+Na) + ] 373.0856, found 373.0860; IR (film): 2980, 1721, 1371, 1152, 1106, 838 cm -1. tert-butyl 2-(4-chlorophenyl)-2-((trifluoromethyl)thio)pent-4-enoate (10c) Yield: 68 mg, 93%, colourless oil; HPLC gave 89% e.e., conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.71 (petroleum:ethyl acetate = 50:1); [α] 20 D = +74.0 o (c 2.60, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.42-7.39 (m, 2H), 7.35-7.32 (m, 2H), 5.97-5.87 (m, 1H), 524-5.19 (m, 2H), 3.23-3.12 (m, 2H), 1.39 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 167.7, 136.9, 133.0, 130.8, 128.8 (q, J = 308.8 Hz, 1C), 127.5, 127.2, 119.1, 83.1, 64.0, 39.3, 26.5; 19 F NMR (CDCl 3, 376 MHz) δ -37.0 (s, 3F); HRMS (ESI, m/z): calcd for C 16 H 18 ClF 3 NaO 2 S [(M+Na) + ] 389.0560, found 389.0563; IR (film): 2984, 1726, 1372, 1151, 1106, 839 cm -1. tert-butyl 2-(4-bromophenyl)-2-((trifluoromethyl)thio)pent-4-enoate (10d) Yield: 80 mg, 98%, colourless oil; HPLC gave 87% e.e., conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.68 (petroleum:ethyl acetate = 50:1); [α] 20 D = +67.0 o (c 3.1, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.50-7.47 (m, 2H), 7.35-7.32 (m, 2H), 5.96-5.86 (m, 1H), 5.24-5.19 (m, 2H), 3.22-3.11 (m, 2H), 1.39 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 168.7, 138.5, 131.8, 131.5, 129.7 (q, J = 308.8 Hz, 1C), 128.5, 122.2, 120.1, 84.1, 65.1, 40.3, 27.5; 19 F NMR (CDCl 3, 376 MHz) δ 26

-37.0 (s, 3F); HRMS (ESI, m/z): calcd for C 16 H 18 BrF 3 NaO 2 S [(M+Na) + ] 433.0055, found 433.0068; IR (film): 2981, 1727, 1371, 1151, 1106, 838 cm -1. tert-butyl 2-(4-bromophenyl)-2-((trifluoromethyl)thio)pent-4-enoate (10e) Yield: 73 mg, 90%, colourless oil; HPLC gave 91% e.e., conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.49 (petroleum:ethyl acetate = 50:1); [α] 20 D = + 78.0 o (c 2.75, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.62-7.58 (m, 4H), 7.53-7.51 (m, 2H), 7.45-7.42 (m, 2H), 7.37-7.33 (m, 1H), 6.01-5.90 (m, 1H), 5.25 (d, J = 5.2 Hz, 1H), 5.21 (s, 1H), 3.30-3.20 (m, 2H), 1.41 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 169.1, 140.7, 140.0, 138.1, 132.2, 129.9 (q, J = 308.9 Hz, 1C), 128.7, 127.5, 127.2, 126.9, 126.9, 119.9, 83.8, 65.3, 40.5, 27.6; 19 F NMR (CDCl 3, 376 MHz) δ -36.9 (s, 3F); HRMS (ESI, m/z): calcd for C 22 H 23 F 3 NaO 2 S [(M+Na) + ] 431.1263, found 431.1262; IR (film): 2980, 1724, 1371, 1149, 1106, 841 cm -1. tert-butyl 2-(4-tolyl)-2-((trifluoromethyl)thio)pent-4-enoate (10f) Yield: 56 mg, 81%, colourless oil; HPLC gave 90% e.e., conditions: Daicel chiral column IC, hexane: i PrOH = 100:0, 1.0 ml/min, 20 wavelength = 210 nm; R f = 0.62 (petroleum:ethyl acetate = 50:1); [α] D = +67.0 o (c 2.08, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.32 (d, J = 8.4 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 5.97-5.87 (m, 1H), 5.22-5.21 (m, 1H), 5.18 (s, 1H), 3.24-3.14 (m, 2H), 2.34 (s, 3H), 1.39 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 169.3, 137.8, 136.1, 132.4, 130.0 (q, J = 308.7 Hz, 1C), 129.0, 126.6, 119.6, 83.6, 65.3, 40.5, 27.6, 21.0; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F); HRMS (ESI, m/z): calcd for C 17 H 21 F 3 NaO 2 S [(M+Na) + ] 369.1106, found 369.1112; IR (film): 2983, 1724, 1371, 1148, 1107, 841 cm -1. tert-butyl 2-(4-methoxyphenyl)-2-((trifluoromethyl)thio)pent-4-enoate (10g) Yield: 33 mg, 52%, colourless oil; HPLC gave 80% e.e., conditions: Daicel chiral column OD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.34 (petroleum:ethyl acetate = 50:1); [α] 20 D = +61.0 o (c 1.60, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.31-7.27 (m, 2H), 6.81-6.78 (m, 2H), 5.90-5.80 (m, 1H), 5.15-5.11 (m, 2H), 3.73 (s, 3H), 3.16-3.06 (m, 2H), 1.32 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 169.4, 159.1, 132.4, 131.0, 129.98 (q, J = 308.7 Hz, 1C), 128.0, 119.6, 113.6, 83.6, 65.3, 55.1, 40.5, 27.6; 19 F NMR (CDCl 3, 376 MHz) δ -37.2 (s, 3F); HRMS (ESI, m/z): calcd for C 17 H 21 F 3 NaO 3 S [(M+Na) + ] 385.1056, found 385.1060; IR (film): 2982, 1724, 1370, 1152, 1107, 837 cm -1. 27

tert-butyl 2-(3-tolyl)-2-((trifluoromethyl)thio)pent-4-enoate (10h) Yield: 63 mg, 91%, colourless oil; HPLC gave 91% e.e., conditions: Daicel chiral column IC, hexane: i PrOH = 100:0, 1.0 ml/min, 20 wavelength = 210 nm; R f = 0.60 (petroleum:ethyl acetate = 50:1); [α] D = +63.0 o (c 1.85, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.18-7.15 (m, 3H), 7.04-7.00 (m, 1H), 5.90-5.79 (m, 1H), 5.14-5.11 (m, 2H), 3.17-3.07 (m, 2H), 2.28 (s, 3H), 1.32 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 169.3, 139.0, 137.9, 132.3, 129.9 (q, J = 308.8 Hz, 1C), 128.8, 128.1, 127.3, 123.7, 119.7, 83.6, 65.4, 40.5, 27.5, 21.4; 19 F NMR (CDCl 3, 376 MHz) δ -37.1(s, 3F); HRMS (ESI, m/z): calcd for C 17 H 21 F 3 NaO 2 S [(M+Na) + ] 369.1106, found 369.1102; IR (film): 2983, 1725, 1371, 1145, 1109, 842 cm -1. tert-butyl 2-(3-methoxyphenyl)-2-((trifluoromethyl)thio)pent-4-enoate (10i) Yield: 67 mg, 93%, colourless oil; HPLC gave 82% ee, conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.49 (petroleum:ethyl acetate = 50:1); [α] 20 D = +56.1 o (c 3.00, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.19 (t, J = 7.2 Hz, 1H), 6.97-6.92 (m, 2H), 6.76 (ddd, J = 0.6, 2.4, 8.3 Hz, 1H), 5.90-5.80 (m, 1H), 5.15-5.14 (m, 1H), 5.11-5.11 (m, 1H), 3.72 (s, 3H), 3.16-3.06 (m, 2H), 1.32 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 169.1, 159.4, 140.6, 132.2, 129.9 (q, J = 308.8 Hz, 1C), 129.2, 119.7, 119.0, 113.2, 112.9, 83.7, 65.4, 55.2, 40.4, 27.5; 19 F NMR (CDCl 3, 376 MHz) δ -37.1 (s, 3F); HRMS (ESI, m/z): calcd for C 17 H 21 F 3 NaO 3 S [(M+Na) + ] 385.1056, found 385.1064;IR (film): 2983, 1724, 1371, 1150, 1109, 841 cm -1. tert-butyl 2-(naphthalen-2-yl)-2-((trifluoromethyl)thio)pent-4-enoate (10j) Yield: 70 mg, 92%, colourless oil; HPLC gave 90% ee, conditions: Daicel chiral column IC, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.54 (petroleum:ethyl acetate = 50:1); [α] 20 D = +105 o (c 2.55, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.79-7.73 (m, 4H), 7.49 (dd, J = 2.0, 8.8 Hz, 1H), 7.44-7.40 (m, 2H), 5.97-5.87 (m, 1H), 5.20-5.15 (m, 2H), 3.32-3.23 (m, 2H), 1.30 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 169.1, 136.5, 132.9, 132.7, 132.2, 129.9 (q, J = 308.8 Hz, 1C), 128.3, 128.2, 127.5, 126.6, 126.3, 125.3, 125.0, 119.9, 83.9, 65.9, 40.3, 27.6; 19 F NMR (CDCl 3, 376 MHz) δ -37.0 (s, 3F); HRMS (ESI, m/z): calcd for C 20 H 21 F 3 NaO 2 S [(M+Na) + ] 405.1106, found 405.1115; IR (film): 2982, 1724, 1371, 1151, 1107, 842 cm -1. 28

tert-butyl 2-(thiophen-3-yl)-2-((trifluoromethyl)thio)pent-4-enoate (10k) Yield: 34 mg, 51%, colourless oil; HPLC gave 90% e.e., conditions: Daicel chiral column IC, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.65 (petroleum:ethyl acetate = 50:1); [α] 20 D = +102 o (c 1.30, CHCl 3 ); 1 H NMR (CDCl 3, 400 MHz) δ 7.25-7.21 (m, 2H), 7.07-7.06 (m, 1H), 5.85-5.75 (m, 1H), 5.15-5.13 (m, 1H), 5.11-5.10 (m, 1H), 3.16-3.06 (m, 2H), 1.34 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 168.5, 139.2, 132.1, 129.8 (q, J = 309.0 Hz, 1C), 126.8, 125.7, 122.8, 119.7, 83.7, 62.1, 41.3, 27.6; 19 F NMR (CDCl 3, 376 MHz) δ -37.5 (s, 3F); HRMS (ESI, m/z): calcd for C 14 H 17 F 3 NaO 2 S 2 [(M+Na) + ] 361.0514, found 361.0519; IR (film): 2985, 1726, 1371, 1150, 1108, 839 cm -1. Ethyl 2-(allylthio)-2-phenylpent-4-enoate (14a) Yield: 49 mg, 89%, colourless oil; HPLC gave 0% e.e., conditions: Daicel chiral column IB, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm; R f = 0.40 (petroleum:ethyl acetate = 30:1); 1 H NMR (CDCl 3, 400 MHz) δ 7.43-7.41 (m, 2H), 7.36-7.32 (m, 2H), 7.28-7.24 (m, 1H), 5.79-5.65 (m, 2H), 5.11 (dd, J = 1.3 Hz, J = 17.0 Hz, 1H), 5.03-4.98 (m, 3H), 4.26 (q, J = 7.1 Hz, 2H), 3.07 (ddd, J = 7.2 Hz, J = 12.7 Hz, J = 59.8 Hz, 2H), 2.89 (dd, J = 0.9 Hz, J = 7.0 Hz, 2H), 1.28 (t, J = 7.1 Hz, 3H); 13 C NMR (CDCl 3, 100 MHz) δ 172.1, 139.0, 133.1, 132.8, 128.1, 127.7, 127.3, 118.7, 117.7, 61.5, 60.6, 43.2, 33.5, 14.0; HRMS (ESI, m/z): calcd for C 16 H 21 O 2 S [(M+H) + ] 277.1257, found: 277.1255; IR (film): 2980, 1725, 1214, 917, 734 cm -1. Ethyl 2-(allylthio)-2-(4-methoxyphenyl)pent-4-enoate (14b) Yield: 40 mg, 66%, colorless oil; HPLC gave 1% e.e., conditions: Daicel chiral column OD-H, hexane: i PrOH = 200:1, 1.0 ml/min, wavelength = 210 nm; R f = 0.26 (petroleum:ethyl acetate = 30:1); 1 H NMR (CDCl 3, 400 MHz) δ 7.37-7.33 (m, 2H), 6.88-6.85 (m, 2H), 5.79-5.66 (m, 2H), 5.11 (dd, J = 1.4 Hz, J = 17.0 Hz, 1H), 5.03-4.99 (m, 3H), 4.25 (q, J = 7.1 Hz, 2H), 3.80 (s, 3H), 3.05 (ddd, J = 7.2 Hz, J = 12.7 Hz, J = 54.8 Hz, 2H), 2.89-2.87 (m, 2H), 1.28 (t, J = 7.1 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 172.2, 158.5, 133.2, 132.9, 130.9, 128.8, 118.5, 117.6, 113.3, 61.4, 60.1, 55.1, 43.1, 33.4, 14.0; HRMS (ESI, m/z): calcd for C 17 H 26 NO 3 S [(M+NH 4 ) + ] 324.1628, found: 324.1625; IR (film): 2979, 1724, 1511, 1251, 1213, 1180, 917, 732 cm -1. Ethyl 2-(allylthio)-2-(2-tolyl)pent-4-enoate (14c) 29

Yield: 33 mg, 57%, colorless oil; HPLC gave 2% e.e., conditions: Daicel chiral column OD-H, hexane: i PrOH = 200:1, 0.3 ml/min, wavelength = 210 nm; R f = 0.34 (petroleum:ethyl acetate = 30:1); 1 H NMR (CDCl 3, 400 MHz) δ 7.61-7.59 (m, 1H), 7.23-7.15 (m, 3H), 5.77-5.64 (m, 2H), 5.12 (dd, J = 1.2 Hz, J = 17.0 Hz, 1H), 5.04-5.00 (m, 3H), 4.28-4.17 (m, 2H), 3.04-2.91 (m, 4H), 2.26 (s, 3H), 1.26 (t, J = 7.1 Hz, 3H) ; 13 C NMR (CDCl 3, 100 MHz) δ 172.1, 136.5, 136.2, 133.2, 132.8, 132.0, 128.0, 127.4, 125.4, 118.3, 117.7, 61.5, 60.3, 41.2, 33.3, 20.4, 14.0; HRMS (ESI, m/z): calcd for C 17 H 23 O 2 S [(M+H) + ] 291.1413, found: 291.1416; IR (film): 2984, 1723, 1219, 1034, 916, 732 cm -1 Methyl (E)-2-(allylthio)-2-styrylpent-4-enoate (14d) Yield: 23 mg, 38%, colorless oil; HPLC gave 3% e.e., conditions: Daicel chiral column OD-H, hexane: i PrOH = 200:1, 0.5 ml/min, wavelength = 210 nm; R f = 0.32 (petroleum:ethyl acetate = 30:1); 1 H NMR (CDCl 3, 400 MHz) δ 7.42-7.40 (m, 2H), 7.33 (t, J = 7.4 Hz, 2H), 7.27-7.24 (m, 1H), 6.72 (d, J = 16.3 Hz, 1H), 6.41 (d, J = 16.3 Hz, 1H), 5.85-5.75 (m, 2H), 5.19-5.05 (m, 4H), 3.78 (s, 3H), 3.30-3.20 (m, 2H), 2.82 (ddd, J = 7.0 Hz, J = 14.2 Hz, J = 40.9 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 172.0, 136.4, 133.4, 132.6, 131.9, 128.5, 127.8, 127.7, 126.5, 118.9, 117.8, 56.7, 52.5, 41.6, 33.3; HRMS (ESI, m/z): calcd for C 17 H 24 NO 2 S [(M+NH 4 ) + ] 306.1522, found: 306.1518; IR (film): 2950, 1726, 1217, 918, 747 cm -1 Methyl (E)-2-(allylthio)-2-styrylpent-4-enoate (14e) Yield: 27 mg, 39%, colorless oil; HPLC gave 3% e.e., conditions: Daicel chiral column AD-H, hexane: i PrOH = 90:10, 1.0 ml/min, wavelength = 210 nm; R f = 0.27 (petroleum:ethyl acetate = 10:1); 1 H NMR (CDCl 3, 400 MHz) δ 8.00 (d, J = 8.3 Hz, 2H),.47 (d, J = 8.3 Hz, 2H), 6.77 (d, J = 16.3 Hz, 1H), 6.53 (d, J = 16.3 Hz, 1H), 5.85-5.73 (m, 2H), 5.19-5.06 (m, 4H), 3.91 (s, 3H), 3.80 (s, 3H), 3.30-3.21 (m, 2H), 2.82 (ddd, J = 7.0 Hz, J = 14.2 Hz, J = 51.1 Hz, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 171.7, 166.6, 140.8, 133.3, 132.3, 131.0, 130.5, 129.8, 129.2, 126.3, 119.1, 117.9, 56.5, 52.6, 52.0, 41.5, 33.3; HRMS (ESI, m/z): calcd for C 19 H 23 O 4 S [(M+H) + ] 347.1312, found: 347.1313; IR (film): 2952, 1720, 1435, 1279, 1214, 1110, 919, 732 cm -1 30

tert-butyl 2-phenyl-2-(vinylthio)pent-4-enoate (16) 52-81% yields, colourless oil; HPLC gave 0-6% e.e., conditions: Daicel chiral column IC, hexane: i PrOH = 98:2, 0.3 ml/min, wavelength = 210 nm; R f = 0.35 (petroleum:ethyl acetate = 50:1); 1 H NMR (CDCl 3, 400 MHz) δ 7.45-7.43 (m, 2H), 7.35-7.31 (m, 2H), 7.26-7.23 (m, 1H), 5.79-5.68 (m, 2H), 5.10 (dd, J = 1.4, 17.0 Hz, 1H), 5.04-5.00 (m, 3H), 3.11 (dd, J = 7.0, 12.6 Hz, 1H), 2.95 (dd, J = 7.3, 12.6 Hz, 1H), 2.85 (d, J = 7.0 Hz, 2H), 1.48 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 170.9, 139.6, 133.3, 133.1, 128.0, 127.7, 127.1, 118.4, 117.6, 81.9, 61.3, 43.0, 33.5, 27.8; HRMS (ESI, m/z): calcd for C 18 H 25 O 2 S [(M+H) + ] 305.1570, found 305.1567; IR (film): 2980, 2109, 1721, 1157, 916, 736, 700 cm -1. tert-butyl 2-(allylthio)-2-(4-fluorophenyl)pent-4-enoate (17a) 59 mg, 96% yield, colourless oil; HPLC gave 1% e.e., conditions: Daicel chiral column AD-H+AD-H, hexane: i PrOH = 100:0, 0.5 ml/min, wavelength = 210 nm; R f = 0.41 (petroleum:ethyl acetate = 50:1); 1 H NMR (CDCl 3, 400 MHz) δ 7.37-7.33 (m, 2H), 6.97-6.92 (m, 2H), 5.71-5.58 (m, 2H), 5.03 (dd, J = 1.2, 17.0 Hz, 1H), 4.97-4.90 (m, 3H), 3.02 (dd, J = 7.0, 12.6 Hz, 1H), 2.88 (dd, J = 7.3, 12.6 Hz, 1H), 2.74 (dq, J = 7.0, 14.2 Hz, 2H), 1.41 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 170.7, 161.6 (d, J = 246.8 Hz, 1C), 135.3 (d, J = 3.1 Hz, 1C), 133.0 (d, J = 26.7 Hz, 1C), 129.6 (d, J = 8.0 Hz, 1C), 118.7, 117.8, 114.9, 114.7, 82.2, 60.7, 43.1, 33.5, 27.8; HRMS (ESI, m/z): calcd for C 18 H 24 FO 2 S [(M+H) + ] 323.1476, found 323.1465; IR (film): 1724, 1509, 1237, 1158, 916, 735 cm -1. tert-butyl 2-(allylthio)-2-(4-methoxyphenyl)pent-4-enoate (17b) 56 mg, 87% yield, colourless oil; HPLC gave 2% e.e., conditions: Daicel chiral column IC, hexane: i PrOH = 200:1, 1.0 ml/min, wavelength = 210 nm; R f = 0.30 (petroleum:ethyl acetate = 50:1); 1 H NMR (CDCl 3, 400 MHz) δ 7.37-7.35 (m, 2H), 6.87-6.85 (m, 2H), 5.80-5.68 (m, 2H), 5.10 (dd, J = 1.3, 17.0 Hz, 1H), 5.05-4.99 (m, 3H), 3.81 (s, 3H), 3.09 (dd, J = 7.0, 12.6 Hz, 1H), 2.95 (dd J =7.3, 12.6 Hz, 1H,) 2.83 (d, J = 7.0 Hz, 2H), 1.48 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 171.1, 158.4, 133.4, 133.2, 131.6, 128.9, 118.3, 117.5, 113.2, 81.8, 60.8, 55.1, 43.0, 33.4, 27.8; HRMS (ESI, m/z): calcd for C 19 H 27 O 3 S [(M+H) + ] 335.1675, found 335.1667; IR (film): 2978, 2109, 1720, 1511, 1250, 1157, 918, 835 cm -1. 31

tert-butyl 2,3-diphenyl-2-((trifluoromethyl)thio)pent-4-enoate (18) 34-72% yield, colourless oil; R f = 0.32 (petroleum:ethyl acetate = 50:1); 1 H NMR (CDCl 3, 400 MHz) δ 7.36-7.15 (m, 5H), 7.14-7.03 (m, 3H), 6.85-6.83 (m, 1.3 H), 6.59-6.57 (m, 0.7 H), 6.10-6.01 (m, 0.7 H), 5.97-5.88 (m, 0.3 H), 5.15-4.99 (m, 2H), 4.40 (d, J = 9.0 Hz, 0.7 H), 4.29 (d, J = 9.2 Hz, 0.3 H), 1.44 (s, 3H), 1.42 (s, 6H); 13 C NMR (CDCl 3, 100 MHz) δ 168.6, 168.6, 138.3, 136.8, 136.0, 135.8, 135.6, 134.2, 130.7, 130.4, 130.2, 129.7, 129.4 (q, J = 310.3 Hz), 129.2 (q, J = 310.5 Hz) 127.9, 127.8, 127.6, 127.5, 127.1, 126.7, 119.2, 118.8, 84.0, 83.5, 68.0, 67.3, 57.9, 57.1, 27.6, 27.6; 19 F NMR (CDCl 3, 376 MHz) δ 35.9-35.9 (m, 3F); HRMS (ESI, m/z): calcd for C 22 H 24 F 3 O 2 S [(M+H) + ] 409.1444 found 409.1437; IR (film): 2982, 1732, 1251, 1155, 1132, 1102,735, 701 cm -1. 7. Crystallographic data of compound 8 and 10j 7.1. Solid state structure of 8 Single crystals of 8 were obtained by dissolving it with least amount of CH 2 Cl 2, then adding same amount of Et 2 O. After that the mixture was evaporated at room temperature. A suitable crystal was selected and the sample was performed at 180 K on a SuperNova diffractometer using graphite-monochromated Cu-Kα radiation (λ = 1.54184 Å). The structures were solved with the Shelxs-97 or Olex2 and refined with the Shelxl refinement package using Least Squares minimization. Refinement was performed on F 2 anisotropically for all the non-hydrogen atoms by the full-matrix least-squares method. The hydrogen atoms were placed at the calculated positions and were included in the structure calculation without further refinement of the parameters. Refined structure and crystallographic parameters are summarized in Supplementary Fig. 1 and Supplementary Tables 2-5. The Diamond diagram was drawn by Diamond 3.1. Data Centre as supplementary publication no. CCDC 1502511. Copies of these data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. 32

Supplementary Figure 1. Diamond diagram of 8. Ellipsoids are set at 65% probability. Supplementary Table 2. Selected crystal data of 8. CCDC 1502511 Empirical formula C 25 H 20 F 3 NO 4 S Formula weight 487.48 Temperature/K 180.01(10) Crystal system triclinic Space group P1 a/å 6.17699(18) b/å 7.7546(3) c/å 23.3736(11) α/ 95.199(3) β/ 94.569(3) γ/ 90.016(3) Volume/Å 3 1111.41(7) Z 2 ρ calc g/cm 3 1.457 μ/mm -1 1.820 F(000) 504.0 Crystal size/mm 3 0.15 0.1 0.1 Radiation Cu-Kα (λ = 1.54184) 2Θ range for data collection/ 7.62 to 133.2 Index ranges -5 h 7, -9 k 8, -25 l 27 Reflections collected 7617 Independent reflections 5224 [R int = 0.0262, R sigma = 0.0351] Data/restraints/parameters 5224/3/669 Goodness-of-fit on F 2 1.067 33

Final R indexes [I>=2σ (I)] R 1 = 0.0410, wr 2 = 0.1049 Final R indexes [all data] R 1 = 0.0433, wr 2 = 0.1075 Largest diff. peak/hole / e Å -3 0.50/-0.28 Flack parameter 0.027(16) Supplementary Table 3. Fractional Atomic Coordinates ( 10 4 ) and Equivalent Isotropic Displacement Parameters (Å 2 10 3 ) for 8. U eq is defined as 1/3 of of the trace of the orthogonalised U IJ tensor. Atom x y z U(eq) S1 6801.4(15) 6827.6(11) 4317.1(5) 30.5(2) O1 7922(4) 9648(3) 5249.5(10) 31.0(6) O2 11142(5) 10308(4) 5732.7(12) 50.7(8) O3 6569(6) 7582(5) 8123.8(14) 59.2(9) O4 3505(6) 7271(6) 7624.9(15) 71.4(11) N1 5410(6) 7669(4) 7679.8(14) 39.9(8) C1 9018(5) 9520(4) 2492.9(14) 23.7(7) C2 10219(5) 10341(4) 2969.4(15) 27.0(7) C3 9581(5) 10311(4) 3524.9(14) 24.8(7) C4 7717(5) 9433(4) 3632.7(14) 22.7(7) C5 6419(6) 8710(5) 3150.9(15) 30.7(8) C6 7051(6) 8763(5) 2601.4(15) 31.2(8) C7 9781(5) 9400(4) 1903.5(15) 25.7(7) C8 8668(7) 8423(6) 1449.9(16) 44(1) C9 9401(7) 8250(6) 899.5(18) 48.4(11) C10 11286(7) 9037(5) 792.1(17) 38.6(9) C11 12424(6) 10028(5) 1232.9(17) 39.3(9) C12 11685(6) 10218(5) 1782.2(16) 36.3(9) C13 7091(5) 9176(4) 4232.9(14) 23.3(7) C14 8701(5) 10023(5) 4710.6(14) 26.4(7) C15 9305(6) 9787(5) 5720.3(16) 30.6(8) C16 9364(7) 5943(5) 4136(2) 42.4(10) C17 4758(5) 9834(4) 4329.1(15) 27.5(7) C18 4594(6) 11763(5) 4336.6(16) 31.0(8) C19 3822(6) 12757(5) 4751.2(18) 38.4(9) C20 8252(6) 9228(5) 6226.3(16) 30.7(8) C21 9391(6) 9463(5) 6769.1(17) 36.1(9) C22 8462(7) 8951(5) 7251.6(16) 38.0(9) 34

C23 6408(6) 8226(5) 7172.5(16) 34.1(8) C24 5250(6) 7991(5) 6643.3(16) 36.9(9) C25 6182(6) 8490(5) 6167.9(16) 34.3(9) S2 8040.0(16) 729.3(11) 9229.7(5) 33.1(2) O5 6988(4) 3496(3) 8364.8(10) 33.5(6) O6 3728(5) 2905(5) 7902.3(13) 59.1(9) O7 11441(6) 5198(5) 5914.8(14) 66.7(10) O8 8656(5) 4132(4) 5397.6(13) 57.1(9) N2 9639(6) 4512(4) 5858.6(14) 42.3(8) C26 5911(6) 4170(4) 11129.6(15) 26.7(7) C27 4681(6) 4800(5) 10668.9(15) 30.7(8) C28 5306(6) 4524(4) 10106.1(15) 28.4(7) C29 7144(5) 3592(4) 9984.6(15) 25.1(7) C30 8427(6) 3034(5) 10454.1(17) 36.4(9) C31 7810(6) 3309(5) 11001.6(17) 37.9(9) C32 5156(6) 4330(4) 11725.0(15) 27.5(7) C33 6304(6) 3570(5) 12175.7(16) 38.9(9) C34 5578(7) 3647(6) 12719.4(17) 43.9(10) C35 3700(6) 4482(5) 12838.3(17) 37.6(9) C36 2516(6) 5246(5) 12401.6(17) 38.5(9) C37 3251(6) 5173(5) 11858.7(16) 36.5(9) C38 7758(5) 3108(4) 9372.8(15) 25.3(7) C39 6119(5) 3786(5) 8918.5(14) 26.6(7) C40 5601(6) 3204(5) 7891.0(16) 33.4(8) C41 5500(8) -103(5) 9400(3) 57.9(14) C42 10095(5) 3735(5) 9289.5(16) 29.4(8) C43 10249(6) 5673(5) 9325.3(17) 33.2(8) C44 10991(6) 6547(5) 8930.8(18) 39.7(9) C45 6734(6) 3444(5) 7362.6(16) 29.2(8) C46 8849(6) 4105(5) 7398.2(16) 36.6(9) C47 9812(6) 4453(5) 6908.5(17) 37.1(9) C48 8638(6) 4111(5) 6383.5(16) 33.5(8) C49 6572(7) 3432(5) 6330.8(17) 38.5(9) C50 5612(6) 3100(5) 6825.9(17) 36.0(9) F5 5320(30) -1770(30) 9336(11) 40(3) F2 9256(13) 4260(13) 4153(3) 33(3) F3 10110(50) 6340(30) 3669(16) 68(7) 35

F1 11060(30) 6520(20) 4580(16) 65(4) F6 4510(18) 554(9) 9790(8) 54(5) F4 3963(18) 72(15) 8869(8) 61(3) F4' 3790(11) 436(13) 9239(11) 75(7) F6' 5500(30) 150(20) 10060(6) 77(5) F5' 5890(30) -1870(30) 9398(9) 33(3) F3' 9390(80) 5930(50) 3509(12) 59(6) F1' 10890(40) 6510(40) 4350(30) 55(7) F2' 9230(50) 4180(40) 4162(11) 91(14) Supplementary Table 4. Bond lengths for 8. Atom Atom Length (Å) Atom Atom Length (Å) S1 C13 1.859(3) S2 C38 1.855(3) S1 C16 1.792(4) S2 C41 1.784(4) O1 C14 1.437(4) O5 C39 1.439(4) O1 C15 1.335(4) O5 C40 1.347(4) O2 C15 1.201(5) O6 C40 1.182(5) O3 N1 1.220(4) O7 N2 1.226(5) O4 N1 1.210(5) O8 N2 1.206(4) N1 C23 1.477(5) N2 C48 1.474(5) C1 C2 1.391(4) C26 C27 1.393(5) C1 C6 1.400(5) C26 C31 1.390(5) C1 C7 1.486(4) C26 C32 1.497(4) C2 C3 1.389(4) C27 C28 1.398(5) C3 C4 1.390(4) C28 C29 1.381(5) C4 C5 1.402(4) C29 C30 1.402(5) C4 C13 1.515(4) C29 C38 1.523(5) C5 C6 1.376(5) C30 C31 1.363(5) C7 C8 1.382(5) C32 C33 1.398(5) C7 C12 1.397(5) C32 C37 1.390(5) C8 C9 1.393(5) C33 C34 1.377(5) C9 C10 1.366(6) C34 C35 1.364(6) C10 C11 1.374(6) C35 C36 1.385(6) C11 C12 1.392(5) C36 C37 1.378(5) C13 C14 1.535(4) C38 C39 1.536(5) C13 C17 1.555(4) C38 C42 1.555(4) C15 C20 1.492(5) C40 C45 1.493(5) 36

C16 F2 1.311(11) C41 F5 1.29(3) C16 F3 1.280(17) C41 F6 1.211(10) C16 F1 1.46(3) C41 F4 1.519(12) C16 F3' 1.47(3) C41 F4' 1.182(10) C16 F1' 1.11(3) C41 F6' 1.537(14) C16 F2' 1.38(3) C41 F5' 1.39(2) C17 C18 1.498(5) C42 C43 1.500(5) C18 C19 1.303(5) C43 C44 1.304(5) C20 C21 1.398(5) C45 C46 1.396(5) C20 C25 1.392(5) C45 C50 1.388(5) C21 C22 1.394(5) C46 C47 1.379(5) C22 C23 1.380(6) C47 C48 1.379(5) C23 C24 1.376(5) C48 C49 1.373(6) C24 C25 1.377(5) C49 C50 1.386(6) Supplementary Table 5. Bond angles for 8 Atom Atom Atom Angle ( o ) Atom Atom Atom Angle ( o ) C16 S1 C13 103.80(17) C41 S2 C38 103.69(18) C15 O1 C14 118.5(3) C40 O5 C39 118.8(3) O3 N1 C23 118.1(3) O7 N2 C48 118.0(3) O4 N1 O3 123.8(3) O8 N2 O7 123.5(4) O4 N1 C23 118.0(3) O8 N2 C48 118.4(4) C2 C1 C6 116.0(3) C27 C26 C32 121.5(3) C2 C1 C7 122.6(3) C31 C26 C27 116.5(3) C6 C1 C7 121.3(3) C31 C26 C32 121.9(3) C3 C2 C1 122.0(3) C26 C27 C28 121.2(3) C2 C3 C4 121.4(3) C29 C28 C27 121.3(3) C3 C4 C5 116.7(3) C28 C29 C30 117.0(3) C3 C4 C13 123.5(3) C28 C29 C38 122.9(3) C5 C4 C13 119.7(3) C30 C29 C38 120.0(3) C6 C5 C4 121.3(3) C31 C30 C29 121.3(3) C5 C6 C1 122.2(3) C30 C31 C26 122.5(3) C8 C7 C1 121.3(3) C33 C32 C26 121.2(3) C8 C7 C12 116.6(3) C37 C32 C26 122.6(3) C12 C7 C1 122.1(3) C37 C32 C33 116.1(3) C7 C8 C9 122.0(4) C34 C33 C32 121.8(4) C10 C9 C8 120.5(4) C35 C34 C33 120.9(4) 37

C9 C10 C11 118.9(4) C34 C35 C36 119.0(4) C10 C11 C12 120.7(4) C37 C36 C35 120.1(4) C11 C12 C7 121.2(3) C36 C37 C32 122.2(3) C4 C13 S1 110.1(2) C29 C38 S2 111.1(2) C4 C13 C14 113.1(3) C29 C38 C39 112.2(3) C4 C13 C17 111.9(3) C29 C38 C42 111.5(3) C14 C13 S1 110.1(2) C39 C38 S2 109.8(2) C14 C13 C17 109.6(3) C39 C38 C42 110.5(3) C17 C13 S1 101.4(2) C42 C38 S2 101.1(2) O1 C14 C13 106.7(3) O5 C39 C38 108.3(3) O1 C15 C20 110.8(3) O5 C40 C45 110.3(3) O2 C15 O1 124.3(3) O6 C40 O5 124.0(3) O2 C15 C20 124.9(3) O6 C40 C45 125.6(3) F2 C16 S1 107.8(4) F5 C41 S2 114.9(10) F2 C16 F1 104.7(8) F5 C41 F4 91.5(12) F2 C16 F3' 96.9(16) F5 C41 F6' 98.4(14) F2 C16 F2' 1.1(14) F5 C41 F5' 15.9(12) F3 C16 S1 117.9(9) F6 C41 S2 122.5(5) F3 C16 F2 111.5(13) F6 C41 F5 113.1(12) F3 C16 F1 103.9(15) F6 C41 F4 103.4(7) F3 C16 F3' 25.0(9) F6 C41 F6' 36.8(5) F3 C16 F2' 112.5(16) F6 C41 F5' 116.7(11) F1 C16 S1 110.3(9) F4 C41 S2 105.0(6) F1 C16 F3' 128.4(17) F4 C41 F6' 139.4(6) F3' C16 S1 106.5(15) F4' C41 S2 124.2(7) F1' C16 S1 119.9(18) F4' C41 F5 106.0(13) F1' C16 F2 113(2) F4' C41 F6 67.1(7) F1' C16 F3 85.9(16) F4' C41 F4 36.3(7) F1' C16 F1 18(3) F4' C41 F6' 103.4(8) F1' C16 F3' 110.6(17) F4' C41 F5' 121.9(12) F1' C16 F2' 113(2) F6' C41 S2 106.1(6) F2' C16 S1 106.9(12) F5' C41 S2 102.5(8) F2' C16 F1 104.5(14) F5' C41 F4 104.8(12) F2' C16 F3' 97.8(19) F5' C41 F6' 93.2(13) C18 C17 C13 112.3(3) C43 C42 C38 111.8(3) C19 C18 C17 124.1(4) C44 C43 C42 124.5(4) C21 C20 C15 118.5(3) C46 C45 C40 121.4(3) 38

C25 C20 C15 121.6(3) C50 C45 C40 119.1(3) C25 C20 C21 120.0(3) C50 C45 C46 119.4(3) C22 C21 C20 120.1(4) C47 C46 C45 120.8(3) C23 C22 C21 117.9(3) C48 C47 C46 118.1(4) C22 C23 N1 118.4(3) C47 C48 N2 118.5(3) C24 C23 N1 118.5(3) C49 C48 N2 118.8(3) C24 C23 C22 123.1(4) C49 C48 C47 122.7(4) C23 C24 C25 118.8(4) C48 C49 C50 118.7(3) C24 C25 C20 120.2(3) C49 C50 C45 120.2(4) 7.2. Solid state structure of 10j Single crystals of 10j were obtained by dissolving it with least amount of Et 2 O, after that the mixture was evaporated at room temperature. A suitable crystal was selected and the sample was performed at 180 K on a SuperNova diffractometer using graphite-monochromated Cu-Kα radiation (λ = 1.54184 Å). The structures were solved with the Shelxs-97 or Olex2 and refined with the Shelxl refinement package using Least Squares minimization. Refinement was performed on F 2 anisotropically for all the non-hydrogen atoms by the full-matrix least-squares method. The hydrogen atoms were placed at the calculated positions and were included in the structure calculation without further refinement of the parameters. Refined structure and crystallographic parameters are summarized in Supplementary Fig. 2 and Supplementary Tables 6-9. The Diamond diagram was drawn by Diamond 3.1. Data Centre as supplementary publication no. CCDC1528864. Copies of these data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary Figure 2. Diamond diagram of 10j. Ellipsoids are set at 65% probability. 39

Supplementary Table 6. Selected crystal data of 10j. CCDC 1528864 Empirical formula C 20 H 21 F 3 O 2 S Formula weight 382.43 Temperature/K 100.0(2) Crystal system orthorhombic Space group P2 1 2 1 2 1 a/å 6.73187(8) b/å 9.48324(13) c/å 29.9037(4) α/ 90 β/ 90 γ/ 90 Volume/Å 3 1909.05(4) Z 4 ρ calc g/cm 3 1.331 μ/mm -1 1.861 F(000) 800.0 Crystal size/mm 3 0.2 0.2 0.1 Radiation Cu-Kα (λ = 1.54184) 2Θ range for data collection/ 5.91 to 133.186 Index ranges -8 h 8, -11 k 11, -35 l 35 Reflections collected 69136 Independent reflections 3360 [R int = 0.1573, R sigma = 0.0352] Data/restraints/parameters 3360/0/238 Goodness-of-fit on F 2 1.054 Final R indexes [I>=2σ (I)] R 1 = 0.0357, wr 2 = 0.0926 Final R indexes [all data] R 1 = 0.0360, wr 2 = 0.0931 Largest diff. peak/hole / e Å -3 0.27/-0.45 Flack parameter -0.008(9) Supplementary Table 7. Fractional Atomic Coordinates ( 10 4 ) and Equivalent Isotropic Displacement Parameters (Å 2 10 3 ) for 10j. U eq is defined as 1/3 of the trace of the 40

orthogonalised U IJ tensor. Atom x y z U(eq) C1 8425(4) 5766(2) 3597.4(6) 20.8(5) C2 9828(4) 5692(3) 3243.1(7) 26.9(5) C3 9474(4) 6356(3) 2845.6(7) 29.2(5) C4 7700(4) 7123(2) 2773.2(7) 27.3(5) C5 7314(4) 7863(3) 2370.3(8) 38.1(6) C6 5586(5) 8589(3) 2316.2(9) 43.4(7) C7 4137(4) 8598(3) 2652.8(9) 39.5(7) C8 4461(4) 7891(3) 3047.2(9) 31.3(5) C9 6263(4) 7161(2) 3118.3(7) 24.1(5) C10 6678(4) 6470(2) 3530.0(7) 22.3(5) C11 8891(3) 5014(2) 4037.6(7) 21.1(5) C12 9000(3) 3410(2) 3941.3(7) 22.6(5) C13 6912(4) 1349(3) 3789.7(7) 27.3(5) C14 7658(4) 510(3) 4184.7(9) 38.3(6) C15 7914(5) 965(3) 3351.3(9) 40.4(7) C16 4676(4) 1247(3) 3753.6(10) 36.5(6) C17 11446(4) 7202(3) 4344.7(8) 32.3(5) C18 7368(3) 5295(3) 4412.1(7) 24.0(5) C19 7766(4) 4510(3) 4839.2(7) 29.2(5) C20 6556(5) 3562(3) 5001.5(8) 39.4(6) F1 10820(3) 8008.7(17) 4008.5(6) 49.5(5) F2 10359(3) 7564(2) 4695.2(6) 60.7(6) F3 13318(2) 7582.1(19) 4432.3(6) 46.7(4) O1 7208(2) 2894.2(17) 3875.0(5) 23.1(4) O2 10549(3) 2780.3(19) 3925.0(6) 34.3(4) S1 11492.0(8) 5349.6(6) 4220.3(2) 26.35(17) Supplementary Table 8. Bond lengths for 10j. Atom Atom Length (Å) Atom Atom Length (Å) C1 C2 1.421(3) C11 S1 1.862(2) C1 C10 1.367(3) C12 O1 1.317(3) C1 C11 1.530(3) C12 O2 1.203(3) C2 C3 1.366(3) C13 C14 1.510(4) 41

C3 C4 1.415(4) C13 C15 1.519(3) C4 C5 1.419(3) C13 C16 1.512(4) C4 C9 1.415(3) C13 O1 1.500(3) C5 C6 1.362(4) C17 F1 1.332(3) C6 C7 1.401(4) C17 F2 1.324(3) C7 C8 1.374(4) C17 F3 1.337(3) C8 C9 1.413(4) C17 S1 1.796(3) C9 C10 1.422(3) C18 C19 1.502(3) C11 C12 1.549(3) C19 C20 1.306(4) C11 C18 1.542(3) Supplementary Table 9. Bond angles for 10j. Atom Atom Atom Angle ( o ) Atom Atom Atom Angle ( o ) C2 C1 C11 118.8(2) C18 C11 S1 112.49(14) C10 C1 C2 119.05(19) O1 C12 C11 110.45(18) C10 C1 C11 122.09(19) O2 C12 C11 122.4(2) C3 C2 C1 120.7(2) O2 C12 O1 127.1(2) C2 C3 C4 121.1(2) C14 C13 C15 113.6(2) C3 C4 C5 122.6(2) C14 C13 C16 110.7(2) C3 C4 C9 118.6(2) C16 C13 C15 111.4(2) C9 C4 C5 118.8(2) O1 C13 C14 109.73(19) C6 C5 C4 120.5(3) O1 C13 C15 108.79(19) C5 C6 C7 120.8(2) O1 C13 C16 101.9(2) C8 C7 C6 120.2(3) F1 C17 F3 106.9(2) C7 C8 C9 120.3(3) F1 C17 S1 114.25(17) C4 C9 C10 119.0(2) F2 C17 F1 105.9(2) C8 C9 C4 119.3(2) F2 C17 F3 107.2(2) C8 C9 C10 121.7(2) F2 C17 S1 115.3(2) C1 C10 C9 121.5(2) F3 C17 S1 106.73(18) C1 C11 C12 107.91(16) C19 C18 C11 114.42(19) C1 C11 C18 114.07(18) C20 C19 C18 123.1(2) C1 C11 S1 111.45(16) C12 O1 C13 120.67(18) C12 C11 S1 100.26(15) C17 S1 C11 102.24(12) C18 C11 C12 109.66(18) 42

8. References 1. Haas, A. & Hinsken, H. Darstellung und charakterisierung von trifluoromethylthiocyclopropanen. J. Fluorine Chem. 28, 303-317 (1985). 2. Haas, A. & Kraechter, H.-U. Darstellung und Reaktionen Trifluormethylchalkogenyl -substituierter Alkine. Chem. Ber. 121, 1833-1840 (1988). 3. Manning, J. R. & Davies H. M. L. One-flask Synthesis of Methyl Arylvinyldiazoacetates and Their Application in Enantioselective C-H Functionalization: Synthesis of (E)-Methyl 2-Diazo-4-Phenylbut-3-Enoate and (S, E)-Methyl 2-[(R)-4-Methyl-1,2-Dihydronaphthalen -2-Yl]-4-Phenylbut-3-Enoate. Org. Synth. 84, 334-346 (2007). 4. Rong, M., Li, D., Huang, R., Huang, Y., Han, X. & Weng, Z. Synthesis of Allylic and Propargylic Trifluoromethyl Thioethers by Copper(I)-Catalyzed Trifluoromethylthiolation of Allylic Bromides and Propargylic Chlorides. Eur. J. Org. Chem. 2014, 5010-5016 (2014). 5. Matheis, C., Wang, M., Krause, T. & Goossen, L. J. Metal-Free Trifluoromethylthiolation of Alkyl Electrophiles via a Cascade of Thiocyanation and Nucleophilic Cyanide CF 3 Substitution. Synlett 26, 1628-1632 (2015). 6. Davies, P. W., Albrecht, S. J.-C. & Assanelli, G. Silver-Catalyzed Doyle Kirmse reaction of allyl and propargyl sulfides. Org. Bio. Chem. 7, 1276-1279 (2009). 7. Barnes, D. M. et al. Development of a Catalytic Enantioselective Conjugate Addition of 1,3-Dicarbonyl Compounds to Nitroalkenes for the Synthesis of Endothelin-A Antagonist ABT-546. Scope, Mechanism, and Further Application to the Synthesis of the Antidepressant Rolipram. J. Am. Chem. Soc. 124, 13097-13105 (2002). 43

9. 1 H, 13 C, 19 F NMR spectra and HPLC data of the products 44

Conditions: Daicel chiral column OJ-H, conditions: hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 45

46

47

Conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0ml/min, wavelength = 210 nm 48

49

Conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0ml/min, wavelength = 210 nm 50

51

52

Conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0ml/min, wavelength = 210 nm 53

54

55

56

57

Conditions: Daicel chiral column OD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 58

59

Conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 60

61

62

Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 63

64

Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 65

66

67

Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 68

69

Conditions: Daicel chiral column OD-H, hexane: i PrOH = 95:5, 1.0 ml/min, wavelength = 210 nm 70

71

72

Conditions: Daicel chiral column IC, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 73

74

Daicel chiral column IC, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 75

76

77

Daicel chiral column OJ-H+OJ, hexane: i PrOH = 100:0, 0.8 ml/min, wavelength = 210 nm 78

79

Conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 80

81

82

Conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 83

84

Conditions: Daicel chiral column OJ-H+OJ, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 85

86

87

Conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 88

89

Conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 90

F 91

92

Conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 93

94

Conditions: Daicel chiral column AD-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 95

96

97

Conditions: Daicel chiral column OJ-H+OJ, hexane: i PrOH = 96:4, 1.0 ml/min, wavelength = 210 nm 98

99

Conditions: Daicel chiral column OD-H+OD-H, hexane: i PrOH = 100:0, 0.6 ml/min, wavelength = 210 nm 100

101

102

Conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 103

104

Conditions: Daicel chiral column OJ-H+OJ, hexane: i PrOH = 94:6, 0.5 ml/min, wavelength = 210 nm 105

106

107

Conditions: Daicel chiral column OJ-H, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 108

109

Conditions: Daicel chiral column IC+IC, hexane: i PrOH = 100:0, 1.0 ml/min, wavelength = 210 nm 110

111