Construction of 1,3-Dithio-Substituted Tetralins by [1,5]-Alkylthio Group Transfer Mediated Skeletal Rearrangement

Construction of 1,3-Dithio-Substituted Tetralins by [1,5]-Alkylthio Group Transfer Mediated Skeletal Rearrangement Naoya Hisano, Yuto Kamei, Yaoki Kansaku, and Keiji Mori * Masahiro Yamanaka, Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei, Tokyo 184-8588, Japan. Department of Chemistry and Research Center for Smart Molecules, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501, Japan k_mori@cc.tuat.ac.jp myamanak@rikkyo.ac.jp Supporting Information Table of contents General experimental procedures Procedure and spectral data DFT calculations Cartesian coordinates References S1 S2 S3 S32 S33 S1

General experimental procedures All reactions utilizing air- and moisture-sensitive reagents were performed in dried glassware under an atmosphere of dry nitrogen. Anhydrous ethereal solvents (THF, Et 2 O) were purchased from Kanto Chemical Co., INC., and used directly. Dichloromethane and 1,2-dichloroethane were distilled over CaH 2. Benzene and toluene were distilled over CaH 2, and stored over 4A molecular sieves. N,N-Dimethylformamide (DMF) was distilled over CaH 2, and stored over 4A molecular sieves. For thin-layer chromatography (TLC) analysis, Merck pre-coated plates (silica gel 60 F 254, Art 5715, 0.25 mm) were used. Column chromatography and preparative TLC (PTLC) were performed on Silica Gel 60N (spherical, neutral), Kanto Chemical Ltd. and Wakogel B-5F, Wako Pure Chemical Industries, respectively. 1 H NMR, 13 C NMR were measured on a AL-300 MR (JEOL Ltd., 300 MHz) and ECX-400 (JEOL Ltd., 400 MHz) spectrometers. Chemical shifts are expressed in parts per million (ppm) downfield from internal standard (tetramethylsilane for 1 H, 0.00 ppm), and coupling constants are reported as hertz (Hz). Splitting patterns are indicated as follows: br, broad; s, singlet; d, doublet; t, triplet; q, quartet; sep, septet; m, multiplet. Infrared (IR) spectra were recorded on a FTIR-8600PC instrument (Shimadzu Co.). Elemental analysis (EA) was carried out on Flash2000 instrument (Amco Inc.). S2

1. Preparation of starting materials. Scheme 1. Preparation of starting materials 3. Preparation of 3a was shown as a representative example. O Br KCN Br NaH, EtO Br O H 2 SO 4 Br O DMF/H 2 O THF H 2 O/ 1.4-dioxane Br CN CN s1 86% s2 s3 65% s4 TiCl 4, EtSH CH 2 Cl 2 Br i) n-buli ii) DMF THF 79% s5 93% O s6 MeO 2 C MeO 2 C AcOH, piperidine Benzene 91% 3a Br CN Synthesis of 2-(2-bromophenyl)acetonitrile (s2): To a solution of 2-bormobenzyl bromide (s1) (1.57 g, 6.26 mmol) in DMF (2.5 ml) and H 2 O (1.6 ml) was added KCN (612 mg, 9.39 mmol) at room temperature. After being stirred for 5 min, the reaction temperature was suddenly warmed up to room temperature. After being stirred for 2 h at room temperature, the reaction was stopped by adding H 2 O. The crude products were extracted with EtOAc (x3) and the combined organic extracts were washed with brine, dried (Na 2 SO 4 ), and concentrated in vacuo. The residue was purified by column chromatography (silica gel, hexane/etoac = 10/1) to give s2 (1.05 g, 86%) as colorless oil. Br O Synthesis of 1-(2-bromophenyl)propan-2-one (s4): To a suspension of NaH (60% oil, 262 mg, 6.01 mmol) in THF (3.0 ml) was added a solution of s2 (1.00 g, 5.15 mmol) in THF (1.0 ml) at 0 C. After being stirred for 1.5 h, a solution of ethyl acetate (0.60 ml, 6.1 mmol) in THF (7.3 ml) was added to the reaction mixture, and then heated reflux. After being stirred for 40 h, the reaction was stopped by adding H 2 O. After separation of organic and aqueous layer, the aqueous layer acidified with 1 M HCl. The crude products were extracted with EtOAc (x3) S3

and the combined organic extracts were washed with brine, dried (Na 2 SO 4 ), and concentrated in vacuo to give crude s3 as brown oil. This material was used next reaction without further purification. A solution of s3 in 1,4-dioxane (2.9 ml) and 60% H 2 SO 4 (8.7 ml) was heated at 105 C. After being stirred for 17 h at 105 C, the reaction was stopped by adding H 2 O at room tempersture. The crude products were extracted with EtOAc (x5) and the combined organic extracts were washed with brine, dried (Na 2 SO 4 ), and concentrated in vacuo. The residue was purified by column chromatography (silica gel, hexane/etoac = 15/1) to give s4 (710 mg, 65%) as yellow oil. 1 H NMR (300 MHz, CDCl 3 ) δ 2.22 (s, 3H), 3.87 (s, 2H), 7.12 7.32 (m, 3H), 7.58 (d, 1H, J = 8.1 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 30.1, 51.0, 125.2, 127.8, 129.1, 131.9, 133.1, 135.0, 205.0. The 1 H and 13 C NMR was in complete agreement with those in the literature. 1 Br Synthesis of (1-(2-Bromophenyl)propane-2,2-diyl)bis(ethylsulfane) (s5): To a solution of s4 (217 mg, 1.02 mmol) in CH 2 Cl 2 (1.0 ml) were successively added EtSH (0.23 ml, 3.10 mmol) and TiCl 4 (1. 0 M in CH 2 Cl 2, 33 µl, 0.33 mmol) at 15 C. After being stirred for 5 min, the reaction temperature was suddenly warmed up to room temperature. After being stirred for 18 h at room temperature, the reaction was stopped by adding H 2 O at 0 C. The crude products were extracted with EtOAc (x3) and the combined organic extracts were washed with brine, dried (Na 2 SO 4 ), and concentrated in vacuo. The residue was purified by column chromatography (silica gel, hexane/etoac = 15/1) to give s5 (256 mg, 79%) as colorless oil. IR (neat) 2967, 2926, 2868, 1469, 1440, 1372, 1262, 1072, 1060, 1046, 1023, 976, 752 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.25 (t, 6H, J = 7.5 Hz), 1.49 (s, 3H), 2.58-2.75 (m, 4H, J = 3.9 Hz), 3.32 (s, 2H), 7.08 (t, 1H, J = 7.8 Hz), 7.24 (t, 1H, J = 7.8 Hz), 7.46 (d, 1H, J S4

= 7.8 Hz), 7.52 (d, 1H, J = 7.8 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 13.9, 23.8, 26.6, 46.0, 60.6, 126.3, 126.7, 128.4, 132.8, 133.0, 136.1. Anal. Calcd for C 13 H 19 BrS 2 : C, 48.90; H, 6.00. Found: C, 48.67; H, 6.29. O Synthesis of 2-(2,2-Bis(ethylthio)propyl)benzaldehyde (s6): To a solution of s5 (185 mg, 0.580 mmol) in THF (2.9 ml) was added n-buli (1.55 M in hexane, 0.47 ml, 0.752 mmol) at 78 C. After being stirred for 15 min, DMF (80 µl, 1.0 mmol) was added to the reaction mixture. After being stirred for 4 h at 78 C, the reaction was stopped by adding saturated aqueous NH 4 Cl at 0 C. The crude products were extracted with EtOAc (x3) and the combined organic extracts were washed with brine, dried (Na 2 SO 4 ), and concentrated in vacuo. The residue was purified by column chromatography (silica gel, hexane/etoac = 8/1) to give s6 (144 mg, 93%) as colorless oil. IR (neat) 2967, 2927, 2868, 1694, 1599, 1449, 1217, 758 cm 1. 1 H NMR (300 MHz, CDCl 3,) δ 1.18 (t, 6H, J = 7.5 Hz), 1.43 (s, 3H), 2.53 (q, 4H, J = 7.5 Hz), 3.54 (s, 2H), 7.34 7.44 (m, 2H), 7.50 (dt, 1H, J = 1.2, 7.8 Hz), 7.86 (d, 1H, J = 7.8 Hz, 1H), 10.31 (s, 1H). 13 C NMR (75 MHz, CDCl 3,) δ 13.8, 23.9, 27.4, 42.4, 59.8, 127.5, 130.2, 132.7, 133.6, 135.5, 138.4, 191.6. Anal. Calcd for C 14 H 20 OS 2 : C, 62.64; H, 7.51. Found: C, 62.73; H, 7.29. MeO 2 C Synthesis of Dimethyl 2-(2-(2,2-bis(ethylthio)propyl)benzylidene)malonate (3a): To a solution of s6 (90.9 mg, 0.339 mmol) in Benzene (4.1 ml) were successively added dimethyl malonate (39 µl, 0.339 mmol), piperidine (39 µl, 0.339 mmol) and AcOH (19 µl, 0.339 mmol), and then the reaction mixture was heated to reflux. After S5

being stirred for 15 h, the reaction was stopped by adding saturated aqueous NaHCO 3 at 0 C. The crude products were extracted with EtOAc (x3) and the combined organic extracts were washed with 1 M aqueous HCl (x6), brine, dried (Na 2 SO 4 ), and concentrated in vacuo. The residue was purified by column chromatography (silica gel, hexane/etoac = 8/1) to give 3a (118 mg, 91%) as yellow amorphous. IR (neat) 2967, 2928, 2870, 1730, 1626, 1436, 1371, 1262, 1220, 1070, 984, 766 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.21 (t, 6H, J = 7.5 Hz), 1.42 (s, 3H), 2.53 2.67 (m, 4H), 3.17 (s, 2H), 3.67 (s, 3H), 3.84 (s, 3H), 7.18 7.35 (m, 3H), 7.40 (d, 1H, J = 7.8 Hz), 8.18 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.8, 23.9, 27.4, 44.7, 52.4, 52.7, 60.5, 127.2, 127.2, 128.0, 129.4, 132.7, 134.0, 136.2, 143.7, 164.3, 166.6. Anal. Calcd for C 19 H 26 O 4 S 2 : C, 59.66; H, 6.85. Found: C, 59.47; H, 6.63. Me I (1-(2-iodo-4-methylphenyl)propane-2,2-diyl)bis(ethylsulfane) (s7). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 15/1). Yield: 830 mg (94%, synthesized from 1-(bromomethyl)-2-iodo-4-methylbenzene 2 ). IR (neat) 2966, 2925, 2868, 1600, 1485, 1445, 1372, 1261, 1061, 1034, 819 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.24 (t, 6H, J = 7.5 Hz), 1.51 (s, 3H), 2.26 (s, 3H), 2.58 2.76 (m, 4H), 3.29 (s, 2H), 7.08 (d, 1H, J = 7.8 Hz), 7.34 (d, 1H, J = 7.8 Hz), 7.67 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.9, 20.3, 23.8, 26.7, 50.1, 60.8, 103.3, 128.5, 131.4, 136.4, 138.5, 140.1. Anal. Calcd for C 14 H 21 IS 2 : C, 44.21; H, 5.57. Found: C, 44.46; H, 5.43. Me O 2-(2,2-Bis(ethylthio)propyl)-5-methylbenzaldehyde (s8). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 530 mg (88%, synthesized from s7). S6

IR (neat) 2967, 2926, 2868, 1686, 1609, 1498, 1448, 1398, 1373, 1261, 1246, 1161, 1072, 838 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.21 (t, 6H, J = 7.5 Hz), 1.45 (s, 3H), 2.40 (s, 3H), 2.52 2.64 (m, 4H), 3.53 (s, 2H), 7.27 (d, 1H, J = 7.8 Hz), 7.34 (d, 1H, J = 7.8 Hz), 7.70 (s, 1H), 10.31 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.8, 20.9, 23.9, 27.4, 42.1, 59.9, 130.5, 133.6, 133.7, 135.2, 135.5, 137.4, 191.9. Anal. Calcd for C 15 H 22 OS 2 : C, 63.78; H, 7.85. Found: C, 63.49; H, 7.64. MeO 2 C Me Dimethyl 2-(2-(2,2-bis(ethylthio)propyl)-5-methylbenzylidene)malonate (3b). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 333 mg (84%, synthesized from s8). IR (neat) 2967, 2927, 2870, 1733, 1626, 1608, 1494, 1436, 1372, 1269, 1230, 1204, 1167, 1070, 986, 837 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.23 (t, 6H, J = 7.5 Hz), 1.42 (s, 3H), 2.30 (s, 3H), 2.49 2.74 (m, 4H), 3.14 (s, 2H), 3.70 (s, 3H), 3.85 (s, 3H), 7.12 (s, 1H), 7.15 (d, 1H, J = 8.1 Hz), 7.28 (d, 1H, J = 8.1 Hz), 8.16 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.8, 21.0, 23.8, 27.3, 44.2, 52.4, 52.7, 60.6, 126.7, 128.4, 130.3, 132.6, 133.2, 133.7, 136.9, 143.7, 164.3, 166.7. Anal. Calcd for C 20 H 28 O 4 S 2 : C, 60.57; H, 7.12. Found: C, 60.71; H, 6.88. MeO Br (1-(2-Bromo-4-methoxyphenyl)propane-2,2-diyl)bis(ethylsulfane) (s9). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 15/1). Yield: 589 mg (72%, synthesized from 2-bromo-1-(bromomethyl)-4-methoxybenzene 1 ). IR (neat) 2966, 2926, 2869, 2834, 1604, 1565, 1493, 1440, 1372, 1319, 1284, 1253, 1240, 1206, 1071, 1060, 1038, 1028, 859, 839, 815, 784 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.19 (t, 6H, J = 7.5 Hz), 1.43 (s, 3H), 2.52 2.71 (m, 4H), 3.20 (s, 2H), 3.72 (s, 3H), 6.76 (dd, 1H, J = 2.7, 8.4 Hz), 7.03 (d, 1H, J = 2.7 Hz), 7.30 S7

(d, 1H, J = 8.4 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 13.9, 23.7, 26.5, 45.2, 55.4, 60.8, 112.9, 117.7, 126.3, 128.0, 133.2, 158.7. Anal. Calcd for C 14 H 21 BrOS 2 : C, 48.13; H, 6.06. Found: C, 48.32; H, 5.78. MeO O 2-(2,2-Bis(ethylthio)propyl)-5-methoxybenzaldehyde (s10). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 312 mg (68%, synthesized from s9). IR (neat) 2966, 2928, 2869, 1686, 1606, 1572, 1497, 1454, 1421, 1398, 1329, 1285, 1260, 1193, 1164, 1072, 1037 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.20 (t, 6H, J = 7.5 Hz), 1.46 (s, 3H), 2.55 (q, 4H, J = 7.5 Hz), 3.46 (s, 2H), 3.85 (s, 3H), 7.08 (dd, 1H, J = 2.7, 8.4 Hz), 7.29 (d, 1H, J = 8.4 Hz), 7.42 (d, 1H, J = 2.7 Hz),, 10.32 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.8, 23.9, 27.6, 41.9, 55.4, 60.0, 112.1, 120.1, 131.0, 134.7, 136.2, 158.9, 191.0. Anal. Calcd for C 15 H 22 O 2 S 2 : C, 60.36; H, 7.43. Found: C, 60.09; H, 7.35. MeO 2 C MeO Dimethyl 2-(2-(2,2-bis(ethylthio)propyl)-5-methoxybenzylidene)malonate (3c). Brown oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 354 mg (63%, synthesized from s10). IR (neat) 2965, 2928, 1730, 1625, 1605, 1570, 1494, 1436, 1371, 1274, 1238, 1203, 1169, 1070, 1038 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.23 (t, 6H, J = 7.5 Hz), 1.42 (s, 3H), 2.52 2.71 (m, 4H), 3.12 (s, 2H), 3.73 (s, 3H), 3.76 (s, 3H), 3.86 (s, 3H), 6.86 6.92 (m, 2H), 7.31 (d, 1H, J = 8.7 Hz), 8.15 (s, 1H). 13 C NMR (75 MHz, CDCl 3,) δ 13.9, 23.8, 27.4, 43.9, 52.6, 52.7, 55.2, 60.7, 112.5, 115.7, 127.2, 128.4, 133.8, 134.7, 143.4, 158.4, 164.3, 166.7. S8

Anal. Calcd for C 20 H 28 O 5 S 2 : C, 58.22; H, 6.84. Found: C, 58.45; H, 7.11. F Br (1-(2-Bromo-4-fluorophenyl)propane-2,2-diyl)bis(ethylsulfane) (s11). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 15/1). Yield: 881 mg (74%, synthesized from 2-bromo-1-(bromomethyl)-4-fluorobenzene 3 ). IR (neat) 2968, 2927, 2969, 1599, 1486, 1446, 1373, 1264, 1231, 1179, 1072, 1059, 1032, 905, 857, 822, 785 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.27 (t, 6H, J = 7.5 Hz), 1.49 (s, 3H), 2.59 2.77 (m, 4H), 3.29 (s, 2H), 7.00 (ddd, 1H, J = 3.0, 6.0, 8.4 Hz), 7.31 (dd, 1H, J = 3.0, 8.4 Hz), 7.46 (dd, 1H, J = 6.0, 8.4 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 13.9, 23.8, 26.5, 45.1, 60.4 (d, J = 1.3 Hz), 113.9 (d, J = 20.4 Hz), 119.8 (d, J = 24.1 Hz), 126.0 (d, J = 9.2 Hz), 132.0 (d, J = 3.1 Hz), 133.7 (d, J = 8.0 Hz), 161.1 (d, J = 248.4 Hz). Anal. Calcd for C 13 H 18 BrFS 2 : C, 46.29; H, 5.38. Found: C, 46.45; H, 5.22. F O 2-(2,2-Bis(ethylthio)propyl)-5-fluorobenzaldehyde (s12). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 677 mg (91%, synthesized from s11). IR (neat) 2968, 2929, 2890, 1608, 1586, 1493, 1455, 1417, 1397, 1374, 1249, 1150, 1072, 1055, 971, 885, 840 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.22 (t, 6H, J = 7.5 Hz), 1.47 (s, 3H), 2.54 (q, 4H, J = 7.5 Hz), 3.49 (s, 2H), 7.24 (ddd, 1H, J = 3.0, 8.4, 9.0 Hz), 7.38 (dd, 1H, J = 3.0, 8.4 Hz), 7.11 (dd, 1H, J = 3.0, 8.4 Hz), 10.3 (d, 1H, J = 2.4 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 13.7, 24.0, 27.7, 42.0, 59.6 (d, J C-F = 1.2 Hz), 115.3 (d, J C-F = 22.2 Hz), 119.9 (d, J C-F = 21.0 Hz), 143.3 (d, J C-F = 3.8 Hz), 135.3 (d, J C-F = 6.8 Hz), 137.0 (d, J C-F = 6.2 Hz), 162.0 (d, J C-F = 247.3 Hz), 189.9 (d, J C-F = 1.8 Hz). Anal. Calcd for C 14 H 19 FOS 2 : C, 58.71; H, 6.69. Found: C, 58.53; H, 6.82. S9

MeO 2 C F Dimethyl 2-(2-(2,2-bis(ethylthio)propyl)-5-fluorobenzylidene)malonate (3d). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 12/1). Yield: 592 mg (90%, synthesized from s12). IR (neat) 2967, 2928, 1731, 1581, 1489, 1436, 1371, 1272, 1231, 1179, 1163, 1069 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.23 (t, 6H, J = 7.5 Hz), 1.43 (s, 3H), 2.61 (q, 4H, J = 7.5 Hz), 3.14 (s, 2H), 3.74 (s, 3H), 3.87 (s, 3H), 6.98 7.10 (m, 2H), 7.34 7.43 (m, 1H), 8.11 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.8, 23.8, 27.4, 43.9, 52.6, 52.8, 60.3, 114.5 (d, J = 22.2 Hz), 116.3 (d, J = 21.0 Hz), 128.1, 131.9 (d, J = 3.7 Hz), 134.3 (d, J = 8.0 Hz), 135.5 (d, J = 8.0 Hz), 142.1, 161.4 (d, J = 245.4 Hz), 164.0, 166.1. Anal. Calcd for C 19 H 25 FO 4 S 2 : C, 56.98; H, 6.29. Found: C, 57.24; H, 6.57. I Me (1-(2-Iodo-5-methylphenyl)propane-2,2-diyl)bis(ethylsulfane) (s13). Colorless solid (purified by silica gel column chromatography, Hexane/EtOAc = 15/1). Yield: 449 mg (93%, synthesized from 2-(bromomethyl)-1-iodo-4-methylbenzene 4 ). IR (neat) 2966, 2925, 2868, 1465, 1445, 1372, 1262, 1071, 1063, 1010, 806 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.24 (t, 6H, J = 7.5 Hz), 1.54 (s, 3H), 2.31 (s, 3H), 2.60 2.79 (m, 4H), 3.31 (s, 2H), 6.76 (dd, 1H, J = 1.8, 8.1 Hz), 7.29 (d, 1H, J = 1.8 Hz), 7.70 (d, 1H, J = 8.1 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 13.9, 21.0, 23.9, 26.8, 50.5, 60.7, 99.3, 129.7, 132.9, 137.4, 139.1, 139.3. Anal. Calcd for C 14 H 21 IS 2 : C, 44.21; H, 5.57. Found: C, 44.12; H, 5.75. O Me 2-(2,2-Bis(ethylthio)propyl)-4-methylbenzaldehyde (s14). S10

Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 290 mg (84%, synthesized from s13). IR (neat) 2967, 2926, 2868, 1689, 1606, 1447, 1373, 1221, 1072, 822 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.20 (t, 6H, J = 7.5 Hz), 1.45 (s, 3H), 2.41 (s, 3H), 2.48 2.66 (m, 4H), 3.53 (s, 2H), 7.17 (s, 1H), 7.22 (d, 1H, J = 7.8 Hz), 7.78 (d, 1H, J = 7.8 Hz), 10.26 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.8, 21.8, 23.9, 27.3, 42.4, 59.8, 128.3, 130.6, 133.1, 134.3, 138.4, 143.6, 191.4. Anal. Calcd for C 15 H 22 OS 2 : C, 63.78; H, 7.85. Found: C, 63.94; H, 7.81. MeO 2 C Me Dimethyl 2-(2-(2,2-bis(ethylthio)propyl)-4-methylbenzylidene)malonate (3e). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 348 mg (85%, synthesized from s14). IR (neat) 2967, 2928, 2870, 1737, 1626, 1608, 1496, 1436, 1372, 1265, 1243, 1218, 1182, 1069, 986, 833 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.23 (t, 6H, J = 7.5 Hz), 1.44 (s, 3H), 2.36 (s, 3H), 2.52-2.71 (m, 4H), 3.16 (s, 2H), 3.71 (s, 3H), 3.85 (s, 3H), 7.05 (d, 1H, J = 8.1 Hz), 7.18 7.28 (m, 2H), 8.17 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.8, 21.5, 23.8, 27.4, 44.7, 52.5, 52.6, 60.5, 126.0, 127.9, 128.1, 130.9, 133.6, 136.2, 139.7, 143.5, 164.5, 167.0. Anal. Calcd for C 20 H 28 O 4 S 2 : C, 60.57; H, 7.12. Found: C, 60.44; H, 6.96. Br MeO (1-(2-Bromo-5-methoxyphenyl)propane-2,2-diyl)bis(ethylsulfane) (s15). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 15/1). Yield: 732 mg (88%, synthesized from commercially available, 1-bromo-2-(bromomethyl)-4-methoxybenzene). IR (neat) 2966, 2927, 1595, 1570, 1470, 1414, 1372, 1299, 1278, 1256, 1239, 1163, 1134, 1065, 1051, 1014, 802 cm 1. S11

1 H NMR (300 MHz, CDCl 3 ) δ 1.24 (t, 6H, J = 7.5 Hz), 1.49 (s, 3H), 2.57 2.76 (m, 4H), 3.27 (s, 2H), 3.77 (s, 3H), 6.66 (dd, 1H, J = 3.0, 9.0 Hz), 7.04 (d, 1H, J = 3.0 Hz), 7.40 (d, 1H, J = 9.0 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 13.9, 23.8, 26.5, 46.1, 55.3, 60.5, 114.2, 116.8, 118.5, 133.1, 136.9, 158.0. Anal. Calcd for C 14 H 21 BrOS 2 : C, 48.13; H, 6.06. Found: C, 48.04; H, 6.25. O MeO 2-(2,2-Bis(ethylthio)propyl)-4-methoxybenzaldehyde (s16). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 486 mg (96%, synthesized from s15). IR (neat) 2967, 2928, 2868, 1684, 1600, 1568, 1496, 1446, 1329, 1290, 1260, 1249, 1222, 1163, 1119, 1104, 1066, 1030, 812 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.22 (t, 6H, J = 7.5 Hz), 1.46 (s, 3H), 2.60 (q, 4H, J = 7.5 Hz), 3.57 (s, 2H), 3.88 (s, 3H), 6.88 6.96 (m, 2H), 7.84 (d, 1H, J = 8.4 Hz), 10.18 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.8, 23.9, 27.2, 42.4, 55.5, 59.8, 112.7, 119.0, 128.9, 133.4, 140.9, 162.8, 190.6. Anal. Calcd for C 15 H 22 O 2 S 2 : C, 60.36; H, 7.43. Found: C, 60.52; H, 7.21. MeO 2 C MeO Dimethyl 2-(2-(2,2-bis(ethylthio)propyl)-4-methoxybenzylidene)malonate (3f). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 265 mg (55%, synthesized from s16). IR (neat) 2966, 2929, 2870, 2840, 1733, 1602, 1567, 1496, 1436, 1373, 1308, 1255, 1216, 1107, 1069, 1034, 986, 942, 830 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.23 (t, 6H, J = 7.5 Hz), 1.44 (s, 3H), 2.56 2.69 (m, 4H), 3.18 (s, 2H), 3.73 (s, 3H), 3.83 (s, 3H), 3.85 (s, 3H), 6.78 (dd, 1H, J = 2.7, 8.7 Hz), 6.95 (d, 1H, J = 2.7 Hz), 7.30 (d, 1H, J = 8.7 Hz), 8.13 (s, 1H). S12

13 C NMR (75 MHz, CDCl 3 ) δ 13.9, 23.9, 27.4, 44.8, 52.4, 52.5, 55.2, 60.3, 112.9, 118.2, 124.9, 126.2, 129.6, 138.5, 142.8, 160.4, 164.6, 167.2. Anal. Calcd for C 20 H 28 O 5 S 2 : C, 58.22; H, 6.84. Found: C, 58.02; H, 6.67. I (1-(3-Iodonaphthalen-2-yl)propane-2,2-diyl)bis(ethylsulfane) (s17). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 15/1). Yield: 674 mg (95%, synthesized from 2-bromomethyl-3-iode-naphthalene 5 ). IR (neat) 3051, 2965, 2925, 2867, 1579, 1489, 1444, 1371, 1261, 1217, 1128, 1070, 971, 879, 743 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.29 (t, 6H, J = 7.5 Hz), 1.56 (s, 3H), 2.63 2.82 (m, 4H), 3.52 (s, 2H), 7.40 7.47 (m, 2H), 7.69 (d, 1H, J = 7.2 Hz), 7.80 (d, 1H, J = 7.2 Hz), 7.95 (s, 1H), 8.41 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.9, 23.9, 26.6, 50.2, 61.0, 101.3, 126.3, 126.5, 126.5, 127.8, 130.4, 132.4, 133.7, 135.5, 138.7. Anal. Calcd for C 17 H 21 IS 2 : C, 49.04; H, 5.08. Found: C, 44.29; H, 4.85. O 3-(2,2-Bis(ethylthio)propyl)-2-naphthaldehyde (s18). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 629 mg (80%, synthesized from s17). IR (neat) 2967, 2926, 2868, 1695, 1628, 1591, 1445, 1372, 1262, 1174, 1071, 893, 748 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.23 (t, 6H, J = 7.5 Hz), 1.48 (s, 3H), 2.53 2.72 (m, 4H), 3.78 (s, 2H), 7.51 7.67 (m, 2H), 7.81 (s, 1H), 7.87 (d, 1H, J = 7.5 Hz), 7.97 (d, 1H, J = 7.5 Hz), 8.36 (s, 1H), 10.38 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.9, 23.9, 27.1, 42.4, 60.2, 126.8, 127.7, 129.1, 129.2, 131.6, 133.0, 133.6, 134.7, 134.9, 192.5. Anal. Calcd for C 18 H 22 OS 2 : C, 67.88; H, 6.96. Found: C, 67.63; H, 7.17. S13

MeO 2 C Dimethyl 2-((3-(2,2-bis(ethylthio)propyl)naphthalen-2-yl)methylene)malonate (3g). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 562 mg (92%, synthesized from s18). IR (neat) 2967, 2927, 1732, 1620, 1436, 1371, 1265, 1227, 1214, 1182, 1070, 749 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.24 (t, 6H, J = 7.5 Hz), 1.49 (s, 3H), 2.55 2.75 (m, 4H), 3.33 (s, 2H), 3.67 (s, 3H), 3.89 (s, 3H), 7.40 7.55 (m, 2H), 7.80 (dd, 2H, J = 8.1, 8.1 Hz), 7.85 (s, 2H), 8.35 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.8, 23.8, 27.4, 44.6, 52.5, 52.7, 60.6, 126.4, 127.2, 127.4, 127.5, 127.9, 128.0, 131.6, 131.9, 132.3, 132.5, 133.3, 143.7, 164.2, 166.7. Anal. Calcd for C 23 H 28 O 4 S 2 : C, 63.86; H, 6.52. Found: C, 63.95; H, 6.74. Br (1-(2-Bromophenyl)butane-2,2-diyl)bis(ethylsulfane) (s19). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 15/1). Yield: 464 mg (76%, synthesized from s2). IR (neat) 3062, 2968, 2927, 2870, 1469, 1438, 1376, 1261, 1048, 1024, 976, 936, 750 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.05 (t, 3H, J = 7.2 Hz), 1.22 (t, 6H, J = 7.5 Hz), 1.84 (q, 2H, J = 7.2 Hz), 2.51 2.68 (m, 4H), 3.34 (s, 2H), 7.09 (dt, 1H, J = 1.5, 7.8 Hz), 7.26 (dt, 1H, J = 1.5, 7.8 Hz), 7.55 (dd, 1H, J = 1.5, 7.8 Hz), 7.60 (dd, 1H, J = 1.5, 7.8 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 9.5, 13.8, 23.4, 31.5, 43.1, 65.1, 126.4, 126.8, 128.3, 132.5, 132.9, 136.5. Anal. Calcd for C 14 H 21 BrS 2 : C, 50.44; H, 6.35. Found: C, 50.71; H, 6.13. O 2-(2,2-Bis(ethylthio)butyl)benzaldehyde (s20). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). S14

Yield: 375 mg (89%, synthesized from s19). IR (neat) 2968, 2929, 2869, 1693, 1599, 1450, 1213, 758 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.04 (t, 6H, J = 7.5 Hz), 1.06 (t, 3H, J = 7.2 Hz), 1.75 (q, 2H, J = 7.2 Hz), 2.09 2.36 (m, 4H), 3.43 (s, 2H), 7.28 7.50 (m, 3H), 7.86 (d, 1H, J = 7.5 Hz), 10.37 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 9.3, 13.5, 23.3, 32.4, 39.4, 64.6, 127.5, 129.2, 132.6, 133.1, 135.8, 139.0, 191.0. Anal. Calcd for C 15 H 22 OS 2 : C, 63.78; H, 7.86. Found: C, 63.88; H, 7.59. MeO 2 C Dimethyl 2-(2-(2,2-bis(ethylthio)butyl)benzylidene)malonate (3h). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 411 mg (90%, synthesized from s20). IR (neat) 2969, 2930, 1730, 1626, 1436, 1374, 1260, 1218, 1068, 984, 944 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.06 (t, 3H, J = 7.2 Hz), 1.16 (t, 6H, J = 7.5 Hz), 1.81 (q, 2H, J = 7.2 Hz), 2.34 2.54 (m, 4H), 3.15 (s, 2H), 3.69 (s, 3H), 3.86 (s, 3H), 7.18 7.36 (m, 3H), 7.48 (d, 1H, J = 7.8 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 9.5, 13.7, 23.3, 32.1, 41.5, 52.4, 52.7, 64.8, 127.0, 127.1, 127.9, 129.3, 132.3, 134.1, 136.5, 144.1, 164.3, 166.7. Anal. Calcd for C 20 H 28 O 4 S 2 : C, 60.57; H, 7.12. Found: C, 60.73; H, 6.85. Br (1-(2-Bromophenyl)pentane-2,2-diyl)bis(ethylsulfane) (s21). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 15/1). Yield: 875 mg (62%, synthesized from s2). IR (neat) 2962, 2928, 2870, 2362, 1470, 1455, 1438, 1025, 748 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 0.88 (t, 3H, J = 7.2 Hz), 1.22 (t, 6H, J = 7.5 Hz), 1.46-1.62 (m, 2H), 1.71 1.82 (m, 2H), 2.60 (q, 4H, J = 7.5 Hz), 3.35 (s, 2H), 7.10 (dt, 1H, J = 1.5, 7.5 Hz), 7.25 (t, 1H, J = 7.5 Hz), 7.56 (t, 2H, 7.5 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 13.8, 14.2, 18.2, 23.4, 41.2, 43.6, 64.5, 126.4, 126.7, S15

128.3, 132.5, 132.9, 136.5. Anal. Calcd for C 15 H 23 BrS 2 : C, 51.86; H, 6.67. Found: C, 51.63; H, 6.86. O 2-(2,2-Bis(ethylthio)pentyl)benzaldehyde (s22). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 699 mg (82%, synthesized from s21). IR (neat) 2962, 2929, 2871, 1694, 1599, 1452, 1213, 759 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 0.91 (t, 3H, J = 7.2 Hz), 1.08 (t, 6H, J = 7.5 Hz), 1.51-1.76 (m, 4H), 2.15 2.41 (m, 4H), 3.49 (s, 2H), 7.33 7.53 (m, 2H), 7.89 (d, 1H, J = 7.5 Hz), 10.40 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.5, 14.1, 18.0, 23.4, 39.9, 42.1, 64.1, 127.4, 129.2, 132.6, 133.1, 135.8, 139.0, 191.0. Anal. Calcd for C 16 H 24 OS 2 : C, 64.82; H, 8.16. Found: C, 65.03.; H, 8.33. MeO 2 C Dimethyl 2-(2-(2,2-bis(ethylthio)pentyl)benzylidene)malonate (3i). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 558 mg (88%, synthesized from s22). IR (neat) 2959, 2931, 2871, 1729, 1625, 1435, 1373, 1261, 1217, 1067, 985, 767 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 0.89 (t, 3H, J = 7.2 Hz), 1.16 (t, 6H, J = 7.2 Hz), 1.50 1.76 (m, 4H), 2.36 2.54 (m, 4H), 3.16 (s, 2H), 3.69 (s, 3H), 3.86 (s, 3H), 7.20 7.36 (m, 3H), 7.47 (d, 1H, J = 7.8 Hz), 8.34 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.7, 14.0, 18.0, 23.3, 41.6, 42.0, 52.3, 52.6, 64.2, 126.9, 127.0, 127.8, 129.3, 132.3, 134.0, 136.5, 143.9, 164.3, 166.6. Anal. Calcd for C 21 H 30 O 4 S 2 : C, 61.43; H, 7.36. Found: C, 61.27; H, 7.59. S16

MeO 2 C Ph Dimethyl 2-(2-(2,2-bis(ethylthio)-2-phenylethyl)benzylidene)malonate (3j). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 247 mg (79%, synthesized from s2). IR (neat) 2966, 2928, 1731, 1625, 1486, 1436, 1373, 1261, 1219, 1099, 1068, 985, 945, 833 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.23 (t, 3H, J = 7.5 Hz), 2.51 2.73 (m, 4H), 3.43 (s, 2H), 3.63 (s, 3H), 3.83 (s, 3H), 6.90 7.00 (m, 1H), 7.06 7.31 (m, 6H), 7.46 (s, 1H), 7.52 7.61 (m, 2H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.3, 24.5, 45.7, 52.2, 52.4, 68.9, 126.7, 126.9, 127.3, 127.4, 128.1, 128.8, 132.3, 133.9, 135.3, 140.8, 143.2, 164.1, 166.5. Anal. Calcd for C 24 H 28 O 4 S 2 : C, 64.83; H, 6.35. Found: C, 64.97; H, 6.54. MeO 2 C H Dimethyl 2-(2-(2,2-bis(ethylthio)ethyl)benzylidene)malonate (3k). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 190 mg (58%, synthesized from s2). IR (neat) 2953, 2926, 1730, 1627, 1435, 1372, 1261, 1215, 1068, 984, 764 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.19 (t, 6H, J = 7.5 Hz), 2.46 2.72 (m, 4H), 3.18 (d, 1H, J = 7.5 Hz), 3.69 (s, 3H), 3.86 (s, 3H), 3.88 (t, 1H, J = 7.5 Hz), 7.18 7.40 (m, 4H), 8.09 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 14.3, 25.0, 41.2, 51.7, 52.4, 52.6, 127.2, 127.9, 128.0, 129.8, 131.2, 132.6, 138.1, 142.4, 164.0, 166.3. Anal. Calcd for C 18 H 24 O 4 S 2 : C, 58.67; H, 6.56. Found: C, 58.41; H, 6.84. EtO 2 C CO 2 Et Diethyl 2-(2-(2,2-bis(ethylthio)propyl)benzylidene)malonate (3l). S17

Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 235 mg (75%, synthesized from s6). IR (neat) 2975, 2929, 2871, 1731, 1627, 1446, 1375, 1349, 1293, 1257, 1217, 1094, 1068, 1023, 764 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.12 (t, 3H, J = 7.2 Hz), 1.23 (t, 6H, J = 7.2 Hz), 1.32 (t, 3H, J = 7.2 Hz), 1.45 (s, 3H), 2.55 2.72 (m, 2H), 3.19 (s, 2H), 4.18 (q, 2H, J = 7.2 Hz), 4.32 (q, 2H, J = 7.2 Hz), 7.20 7.28 (m, 2H), 7.33 (dd, 1H, J = 7.8, 7.8 Hz), 7.42 (d, 1H, J = 7.8 Hz), 8.18 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.7, 13.8, 14.1, 23.8, 27.4, 44.7, 60.4, 61.3, 61.5, 127.0, 128.1, 128.2, 129.1, 132.5, 134.1, 136.0, 143.0, 163.8, 166.0. Anal. Calcd for C 21 H 30 O 4 S 2 : C, 61.43; H, 7.36. Found: C, 61.59; H, 7.11. Br SPr SPr (1-(2-Bromophenyl)propane-2,2-diyl)bis(propylsulfane) (s23). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 15/1). Yield: 458 mg (71%, synthesized from s4). IR (neat) 2961, 2927, 2871, 1468, 1438, 1372, 1059, 1046, 1023, 751 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.03 (t, 6H, J = 7.5 Hz), 1.50 (s, 3H), 1.64 (sext, 4H, J = 7.5 Hz), 2.58 2.74 (m, 4H), 3.33 (s, 2H), 7.10 (dt, 1H, J = 1.5, 7.8 Hz), 7.26 (dt, 1H, J = 1.5, 7.8 Hz), 7.49 (dd, 1H, J = 1.5, 7.8 Hz), 7.55 (dd, 1H, J = 1.5, 7.8 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 14.0, 22.5, 26.6, 31.9, 45.9, 60.5, 126.3, 126.7, 128.4, 132.8, 133.1, 136.1. Anal. Calcd for C 15 H 23 BrS 2 : C, 51.86; H, 6.67. Found: C, 51.64; H, 6.91. O SPr SPr 2-(2,2-Bis(propylthio)propyl)benzaldehyde (s24). Yellow oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 336 mg (90%, synthesized from s23). IR (neat) 2961, 2928, 2871, 1694, 1599, 1454, 1373, 1290, 1218, 1202, 1185, 1066, 757 cm 1. S18

1 H NMR (300 MHz, CDCl 3 ) δ 0.99 (t, 6H, J = 7.5 Hz), 1.45 (s, 3H), 1.58 (sext, 4H, J = 7.5 Hz), 2.54 (t, 4H, J = 7.5 Hz), 3.58 (s, 2H), 7.38 7.48 (m, 2H), 7.54 (dt, 1H, J = 1.2, 7.5 Hz), 7.90 (dd, 1H, J = 1.2, 7.5 Hz), 10.36 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.94, 22.4, 27.5, 31.9, 42.5, 59.8, 127.5, 130.1, 132.8, 133.6, 135.4, 138.5, 191.7. Anal. Calcd for C 16 H 24 OS 2 : C, 64.82; H, 8.16. Found: C, 64.57; H, 8.01. MeO 2 C SPr SPr Dimethyl 2-(2-(2,2-bis(propylthio)propyl)benzylidene)malonate (3m). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 366 mg (57%, synthesized from s24). IR (neat) 2960, 2929, 2871, 1730, 1626, 1436, 1371, 1291, 1292, 1220, 1069, 767 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.00 (t, 6H, J = 7.2 Hz), 1.43 (s, 3H), 1.61 (sext, 4H, J = 7.2 Hz), 2.51 2.67 (m, 4H), 3.19 (s, 2H), 3.70 (s, 3H), 3.86 (s, 3H), 7.20 7.38 (m, 3H), 7.43 (d, 1H, J = 7.5 Hz), 8.21 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 13.9, 22.4, 27.4, 31.8, 44.6, 52.4, 52.6, 60.4, 127.1, 127.2, 127.9, 129.3, 132.7, 133.9, 136.1, 143.7, 164.2, 166.6. Anal. Calcd for C 21 H 30 O 4 S 2 : C, 61.43; H, 7.36. Found: C, 61.53; H, 7.14. Br Si-Pr Si-Pr (1-(2-Bromophenyl)propane-2,2-diyl)bis(isopropylsulfane) (s25). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 15/1). Yield: 734 mg (32%, synthesized from s4). IR (neat) 2956, 2925, 2862, 1438, 1365, 1241, 1154, 1043, 1023, 752 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.26 (d, 6H, J = 6.9 Hz), 1.31 (d, 6H, J = 6.9 Hz), 1.50 (s, 3H), 3.14 (sept, 2H, J = 6.9 Hz), 3.36 (s, 2H), 7.04 (dd, 1H, J = 7.5 Hz), 7.19 (dd, 1H, J = 7.5 Hz), 7.49 (dd, 2H, J = 7.5 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 25.6, 25.8, 27.5, 34.9, 48.0, 62.1, 126.3, 126.7, 128.4, 132.8, 133.1, 136.3. Anal. Calcd for C 15 H 23 BrS 2 : C, 51.86; H, 6.67. Found: C, 51.89; H, 6.41. S19

O Si-Pr Si-Pr 2-(2,2-Bis(isopropylthio)propyl)benzaldehyde (s26). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 551 mg (84%, synthesized from s25). IR (neat) 2958, 2925, 2864, 1695, 1599, 1450, 1383, 1368, 1291, 1240, 1219, 1201, 1185, 1156, 1070, 1047, 809, 758 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.26 (d, 6H, J = 6.9 Hz), 1.34 (d, 6H, J = 6.9 Hz), 1.52 (s, 3H), 3.04 3.15 (m, 2H), 3.67 (s, 2H), 7.23 (d, 2H, J = 7.5 Hz), 7.47 7.58 (m, 1H), 7.88 (d, 1H, J = 7.5 Hz), 10.37 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 25.5, 25.7, 28.1, 35.0, 44.2, 61.4, 127.5, 130.5, 132.8, 133.7, 135.3, 138.6, 192.0. Anal. Calcd for C 16 H 24 OS 2 : C, 64.82; H, 8.16. Found: C, 64.63; H, 8.39. MeO 2 C Si-Pr Si-Pr Dimethyl 2-(2-(2,2-bis(isopropylthio)propyl)benzylidene)malonate (3l). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 486 mg (34%, synthesized from s26). IR (neat) 2956, 2925, 2864, 1732, 1627, 1436, 1366, 1263, 1221, 1184, 1156, 1070, 766 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.22 (d, 6H, J = 6.9 Hz), 1.27 (d, 6H, J = 6.9 Hz), 1.42 (s, 2H), 3.05 (septet, 2H, J = 6.9 Hz), 3.21 (s, 2H), 3.63 (s, 3H), 3.80 (s, 3H), 7.12 7.32 (m, 3H), 7.44 (d, 1H, J = 7.5 Hz), 8.13 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 25.6, 25.6, 28.3, 35.0, 46.7, 52.4, 52.7, 62.0, 127.2, 127.2, 127.9, 129.4, 132.8, 133.8, 136.3, 143.8, 164.2, 166.6. Anal. Calcd for C 21 H 30 O 4 S 2 : C, 61.43; H, 7.36. Found: C, 61.23; H, 7.31. S20

Br S S 2-(2-Bromobenzyl)-2-methyl-1,3-dithiane (s27). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 20/1). Yield: 310 mg (94%, synthesized from s4). IR (neat) 2903, 1469, 1437, 1422, 1370, 1276, 1061, 1046, 1022, 906, 753 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.61 (s, 3H), 1.91 2.13 (m, 2H), 2.84-3.05 (m, 4H), 3.51 (s, 2H), 7.11 (ddd, 1H, J = 1.8, 7.5, 7.5 Hz), 7.26 (ddd, 1H, J = 1.8, 7.5, 7.5 Hz), 7.46 (dd, 1H, J = 1.8, 7.5 Hz), 7.57 (dd, 1H, J = 1.8, 7.5 Hz),. 13 C NMR (75 MHz, CDCl 3 ) δ 25.0, 26.9, 26.9, 45.5, 59.5, 126.3, 126.6, 128.5, 132.9, 133.0, 135.8. Anal. Calcd for C 12 H 15 BrS 2 : C, 47.52; H, 4.99. Found: C, 47.78; H, 4.91. O S S 2-((2-Methyl-1,3-dithian-2-yl)methyl)benzaldehyde (s28). Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 275 mg (64%, synthesized from s27). IR (neat) 2905, 2862, 2829, 1693, 1598, 1574, 1448, 1421, 1370, 1290, 1277, 1220, 1202, 1186, 759 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.51 (s, 3H), 1.88 2.03 (m, 2H), 2.83 2.91 (m, 4H), 3.74 (s, 2H), 7.39 7.48 (m, 2H), 7.54 (ddd, 1H, J = 1.5, 7.5, 7.5 Hz), 7.88 (dd, 1H, J = 1.5, 7.5 Hz), 10.33 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 24.8, 26.8, 27.7, 42.0, 49.4, 127.6, 130.6, 132.8, 133.8, 135.5, 138.0, 192.0. Anal. Calcd for C 13 H 16 OS 2 : C, 61.86; H, 6.39. Found: C, 61.75; H, 6.11. O O MeO OMe S S Dimethyl 2-(2-((2-methyl-1,3-dithian-2-yl)methyl)benzylidene)malonate (3o). S21

Colorless oil (purified by silica gel column chromatography, Hexane/EtOAc = 10/1). Yield: 305 mg (74%, synthesized from s28). IR (neat) 2951, 1729, 1625, 1436, 1369, 1263, 1221, 1109, 1070, 984, 767 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 1.49 (s, 3H), 1.95 2.05 (m, 2H), 2.80 3.02 (m, 4H), 3.36 (s, 2H), 3.70 (s, 3H), 3.86 (s, 3H), 7.24 7.35 (m, 3H), 7.42 (d, 1H, J = 8.1 Hz), 8.19 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 24.9, 26.8, 27.5, 44.0, 49.8, 52.5, 52.7, 127.2, 127.3, 128.0, 129.3, 132.8, 134.0, 135.8, 143.7, 164.3, 166.6. Anal. Calcd for C 18 H 22 O 4 S 2 : C, 58.99; H, 6.05. Found: C, 59.26; H, 6.01. S22

2. Synthesis of 1,3-dithiotetralin derivatives. General Procedure of skeletal rearrangement involving [1,5]-alkylthio group transfer/cyclization sequence. To a solution of thio ketals 3 (0.10 mmol) in ClCH 2 CH 2 Cl (1.0 ml) was added Sc(OTf) 3 (0.010 mmol, 10 mol%) at room temperature. After completion of the reaction, the reaction was stopped by adding saturated aqueous NaHCO 3. The crude products were extracted with EtOAc (x3) and the combined organic extracts were washed with brine, dried (Na 2 SO 4 ), and concentrated in vacuo. The residue was purified by preparative TLC to give 1,3-dithiotetralin derivatives 4. CO2 Me Dimethyl 1,3-bis(ethylthio)-3-methyl-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4a). Yellow oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 37.0 mg (88%, d.r. = 1:1.5). * shows the peaks of minor diastereomer. IR (neat) 2951, 2928, 2870, 1762, 1736, 1494, 1451, 1433, 1377, 1266, 1219, 1121, 1107, 1046, 959, 914, 786 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 1.09 1.37 (m, 6+6*H), 1.74* (s, 3H), 1.79 (s, 3H), 2.43 3.00 (m, 5+5*H), 3.05 (d, 1H, J = 17.6 Hz), 3.35* (d, 1H, J = 17.6 Hz), 3.66* (s, 3H), 3.73 (s, 3H), 3.74 (s, 3H), 3.87* (s, 3H), 4.51 (s, 1H), 5.03* (s, 1H), 6.90 7.26 (m, 3H+3H*), 7.66 (d, 1H, J = 8.0 Hz), 7.79* (d, 1H, J = 8.0 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 13.8, 13.8, 14.5, 14.6, 22.8, 23.8, 24.9, 26.5, 29.4, 32.1, 42.0, 43.6, 47.5, 49.9, 50.5, 51.1, 52.0, 52.1, 52.5, 52.7, 68.8, 68.9, 126.4, 126.5, 126.6, 126.8, 128.0, 128.1, 128.5, 128.6, 132.2, 133.3, 136.7, 138.4, 168.2, 168.6, 169.6, 170.1. Anal. Calcd for C 19 H 26 O 4 S 2 : C, 59.66; H, 6.85. Found: C, 59.49; H, 6.94. S23

Me CO2 Me Dimethyl 1,3-bis(ethylthio)-3,7-dimethyl-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4b). Colorless oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 30.1 mg (76%, d.r. = 1:1.5). * shows the peaks of minor diastereomer. IR (neat) 2951, 2927, 1762, 1735, 1505, 1433, 1377, 1267, 1217, 1047, 812 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 1.09 1.37 (m, 6+6*H), 1.74* (s, 3H), 1.79 (s, 3H), 2.33 (s, 3H), 2.34* (s, 3H), 2.45 3.05 (m, 6+5*H), 3.28* (d, 1H, J = 17.6 Hz), 3.67* (s, 3H), 3.73 (s, 3H), 3.75 (s, 3H), 3.84* (s, 3H), 4.48 (s, 1H), 5.00* (s, 1H), 6.81 6.96 (m, 2H+2H*), 7.44 (s, 1H), 7.59* (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 13.8, 13.9, 14.5, 14.6, 21.3, 21.4, 22.8, 23.8, 24.9, 26.4, 29.5, 32.3, 41.7, 43.3, 47.6, 50.1, 50.6, 51.2, 51.9, 52.1, 52.5, 52.7, 68.8, 68.9, 127.5, 127.7, 127.9, 128.0, 128.8, 129.0, 129.1, 130.2, 136.0, 136.2, 136.4, 138.2, 168.2, 168.6, 169.6, 170.1. Anal. Calcd for C 20 H 28 O 4 S 2 : C, 60.57; H, 7.12. Found: C, 60.51; H, 7.32. MeO CO2 Me Dimethyl 1,3-bis(ethylthio)-7-methoxy-3-methyl-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4c). Yellow oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 31.1 mg (82%, d.r. = 1:1.6). * shows the peaks of minor diastereomer. IR (neat) 2951, 2928, 1734, 1611, 1504, 1433, 1377, 1242, 1037, 802 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 1.09 1.35 (m, 6H+6H*), 1.74* (s, 3H), 1.79 (s, 3H), 2.45 3.05 (m, 6+5*H), 3.25* (d, 1H, J = 16.8 Hz), 3.67* (s, 3H), 3.74 (s, 6H), 3.76 (s, 3H), 3.80 (s, 3H), 3.81* (s, 3H), 3.84* (s, 3H), 4.47 (s, 1H), 5.01* (s, 1H), 6.68 6.77 (m, 1+1*H), 6.86 (d, 1H, J = 7.6 Hz), 6.89* (d, 1H, J = 7.6 Hz), 7.21 (d, 1H, J = 2.0 Hz), S24

7.38* (d, 1H, J = 2.0 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 13.8, 14.7, 14.8, 22.8, 23.8, 24.8, 26.4, 29.4, 32.2, 41.3, 43.0, 47.8, 50.4, 50.8, 51.4, 52.0, 52.2, 52.5, 52.7, 55.1, 68.7, 68.9, 112.9, 113.0, 113.3, 113.5, 124.6, 125.5, 128.9, 129.0, 137.9, 139.5, 158.2, 158.2, 168.2, 168.6, 169.5, 170.1. Anal. Calcd for C 20 H 28 O 5 S 2 : C, 58.22; H, 6.84. Found: C, 58.47; H, 6.71. F CO2 Me Dimethyl 1,3-bis(ethylthio)-7-fluoro-3-methyl-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4d). Yellow oil (purified by preparative TLC, Hexane/EtOAc = 5/1).. Yield: 33.2 mg (92%, d.r. = 1:1.5). * shows the peaks of minor diastereomer. IR (neat) 2952, 2929, 1763, 1734, 1613, 1499, 1434, 1378, 1261, 1238, 1217, 1144, 1094, 1047, 735 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 1.09 1.35 (m, 6H+6H*), 1.74* (s, 3H), 1.80 (s, 3H), 2.45 3.05 (m, 6+5*H), 3.26* (d, 1H, J = 17.2 Hz), 3.67* (s, 3H), 3.75 (s, 3H), 3.75 (s, 3H), 3.85* (s, 3H), 4.45 (s, 1H), 5.00* (s, 1H), 6.80 6.99 (m, 2+2*H), 7.36 (dd, 1H, J = 2.0, 10.4 Hz), 7.54* (dd, 1H, J = 2.0, 10.4 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 13.8, 13.8, 14.5, 14.6, 22.8, 23.8, 24.8, 26.4, 29.5, 32.2, 41.2, 43.0, 47.5, 50.0, 50.7, 51.0, 52.0, 52.2, 52.6, 52.8, 68.5, 68.6, 113.7 (d, J C-F = 25.7 Hz), 114.0 (d, J C-F = 25.8 Hz), 115.0 (d, J C-F = 22.9 Hz), 115.2 (d, J C-F = 22.9 Hz), 127.9 (d, J C-F = 3.0 Hz), 128.9 (d, J C-F = 2.9 Hz), 129.3 (d, J C-F = 8.5 Hz), 129.5 (d, J C-F = 8.6 Hz), 139.1 (d, J C-F = 7.6 Hz), 140.8 (d, J C-F = 7.6 Hz), 161.5 (d, J C-F = 242.2 Hz), 168.0, 168.5, 169.4, 170.0. Anal. Calcd for C 19 H 25 FO 4 S 2 : C, 56.98; H, 6.29. Found: C, 56.73; H, 6.15. CO2 Me Me S25

Dimethyl 1,3-bis(ethylthio)-3,6-dimethyl-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4e). Colorless oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 29.3 mg (74%, d.r. = 1:1.5). * shows the peaks of minor diastereomer. IR (neat) 2951, 2926, 1762, 1735, 1502, 1432, 1376, 1265, 1216, 1047, 959, 821 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 1.09 1.33 (m, 6H+6H*), 1.73* (s, 3H), 1.78 (s, 3H), 2.26 (s, 3H), 2.28* (s, 3H), 2.45 3.07 (m, 6+5*H), 3.32* (d, 1H, J = 17.2 Hz), 3.67* (s, 3H), 3.73 (s, 6H), 3.83* (s, 3H), 4.48 (s, 1H), 4.99* (s, 1H), 6.74 (s, 1H), 6.77* (s, 1H), 7.03 (d, 1H+1H*, J = 7.6 Hz), 7.53 (d, 1H, J = 7.6 Hz), 7.65* (d, 1H, J = 7.6 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 13.8, 13.9, 14.6, 14.6, 20.9, 22.8, 23.8, 24.9, 26.4, 29.3, 29.7, 32.1, 42.1, 43.7, 47.6, 49.8, 50.4, 51.0, 51.9, 52.1, 52.5, 52.7, 68.8, 68.9, 127.5, 127.8, 128.3, 128.5, 128.5, 128.6, 131.9, 133.0, 133.5, 135.4, 136.0, 136.1, 168.2, 168.6, 169.6, 170.1. Anal. Calcd for C 20 H 28 O 4 S 2 : C, 60.57; H, 7.12. Found: C, 60.71; H, 7.03. MeO Dimethyl 1,3-bis(ethylthio)-6-methoxy-3-methyl-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4f). CO2 Me Colorless oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 31.3 mg (79%, d.r. = 1:1.5). * shows the peaks of minor diastereomer. IR (neat) 2951, 2928, 1734, 1610, 1500, 1432, 1377, 1271, 1237, 1216, 1048, 819 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 1.09 1.35 (m, 6H+6H*), 1.74* (s, 3H), 1.78 (s, 3H), 2.45 3.10 (m, 6+5*H), 3.38* (d, 1H, J = 17.2 Hz), 3.67* (s, 3H), 3.74 (s, 6H), 3.76 (s, 3H), 3.78 (s, 3H), 3.81* (s, 3H), 3.84* (s, 3H), 4.48 (s, 1H), 4.99* (s, 1H), 6.47 (d, 1H, J = 2.4 Hz), 6.51* (d, 1H, J = 2.4 Hz), 6.81 (d, 1+1*H, J = 2.4, 8.4 Hz), 7.57 (d, 1H, J = 8.4 Hz), 7.70* (d, 1H, J = 8.4 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 13.8, 13.9, 14.6, 22.8, 23.8, 24.9, 26.4, 29.2, 31.9, 42.4, 44.0, 47.5, 49.5, 50.4, 50.8, 52.0, 52.1, 52.5, 52.7, 55.2, 68.8, 68.8, 112.5, 112.5, 112.7, S26

113.3, 128.6, 129.7, 130.0, 130.4, 133.5, 134.5, 157.9, 158.0, 168.3, 168.6, 169.6, 170.1. Anal. Calcd for C 20 H 28 O 5 S 2 : C, 58.22; H, 6.84. Found: C, 58.29; H, 6.96. CO2 Me Dimethyl 1,3-bis(ethylthio)-3-methyl-3,4-dihydroanthracene-2,2(1H)-dicarboxylate (4g). Yellow oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 45.0 mg (99%, d.r. = 1:1.6). * shows the peaks of minor diastereomer. IR (neat) 2951, 1760, 1733, 1506, 1432, 1376, 1254, 1220, 1047, 877 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 1.05 1.42 (m, 6+6*H), 1.78* (s, 3H), 1.84 (s, 3H), 2.45 3.56 (m, 6+6*H), 3.28* (d, 1H, J = 17.6 Hz), 3.64* (s, 3H), 3.75 (s, 3H), 3.76 (s, 3H), 3.88* (s, 3H), 4.73 (s, 1H), 5.24* (s, 1H), 7.35 7.90 (m, 5H+5H*), 8.20 (s, 1H), 8.35* (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 13.7, 13.8, 14.6, 14.8, 22.8, 23.8, 24.8, 26.6, 29.5, 32.1, 41.9, 43.8, 47.9, 50.6, 51.1, 51.3, 52.0, 52.2, 52.6, 52.7, 69.1, 69.3, 125.3, 125.3, 125.7, 125.7, 126.3, 126.5, 126.7, 126.8, 127.3, 127.4, 127.7, 127.8, 131.1, 132.0, 132.4, 132.5, 132.6, 132.7, 135.6, 137.2, 168.2, 168.7, 169.4, 170.2. Anal. Calcd for C 23 H 28 O 4 S 2 : C, 63.86; H, 6.52. Found: C, 63.95; H, 6.78. CO2 Me EtS Dimethyl 3-ethyl-1,3-bis(ethylthio)-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4h). Colorless oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 30.2 mg (74%, d.r. = 1:1.9). * shows the peaks of minor diastereomer. IR (neat) 2954, 2928, 1761, 1734, 1451, 1433, 1262, 1232, 1214, 1157, 1051, 785 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 1.01 1.45 (m, 9H+9H*), 1.80 1.93* (m, 1H), 2.02 S27

2.10* (m, 1H), 2.01 3.60 (m, 8H+6H*), 3.61* (s, 3H), 3.71 (s, 3H), 3.75 (s, 3H), 3.82* (s, 3H), 4.61 (s, 1H), 5.22* (s, 1H), 6.93 7.30 (m, 3H+3H*), 7.58 (d, 1H, J = 7.6 Hz), 7.84* (d, 1H, J = 7.6 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 8.6, 8.8, 13.6, 13.7, 14.4, 14.7, 23.4, 24.5, 27.4, 29.4, 29.6, 31.9, 38.2, 38.6, 51.0, 51.4, 51.9, 52.1, 52.4, 52.4, 52.7, 56.2, 69.3, 69.9, 126.5, 126.5, 126.9, 128.1, 128.1, 128.2, 128.5, 131.8, 132.9, 137.0, 138.7, 168.2, 169.1, 169.7, 170.5. Anal. Calcd for C 20 H 28 O 4 S 2 : C, 60.57; H, 7.12. Found: C, 60.31; H, 6.95. CO2 Me Dimethyl 1,3-bis(ethylthio)-3-propyl-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4i). Colorless oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 20.9 mg (52%, d.r. = 1:2.0). Two diastereomers (4ia and 4ib) could be separated. For 4ia. IR (neat) 2957, 2928, 2871, 1762, 1733, 1451, 1432, 1231, 1058, 975, 746 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 0.95 (t, 3H, J = 7.6 Hz), 1.10 (t, 3H, J = 7.6 Hz), 1.28 (t, 3H, J = 7.6 Hz), 1.32 1.48 (m, 1H), 1.66 1.80 (m, 2H), 2.32 2.45 (m, 1H), 2.50 2.66 (m, 2H), 2.68 2.85 (m, 2H), 2.88 3.01 (m, 1H), 3.22 (d, 1H, J = 17.2 Hz), 3.72 (s, 3H), 3.76 (s, 3H), 4.61 (s, 1H), 6.94 (d, 1H, J = 7.6 Hz), 7.10 (dd, 1H, J = 7.6, 7.6 Hz), 7.22 (dd, 1H, J = 7.6 Hz), 7.59 (d, 1H, J = 7.6 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 13.6, 14.4, 14.5, 17.4, 24.5, 31.9, 37.1, 38.9, 51.0, 51.9, 52.0, 52.7, 70.0, 126.5, 126.8, 128.1, 128.5, 132.0, 138.7, 168.2, 170.5. Anal. Calcd for C 21 H 30 O 4 S 2 : C, 61.43; H, 7.36. Found: C, 61.27; H, 7.44. For 4ib. IR (neat) 2957, 2928, 2871, 1732, 1451, 1432, 1246, 1047, 747 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 0.96 (t, 3H, J = 7.6 Hz), 1.07 (t, 3H, J = 7.6 Hz), 1.28 (t, 3H, J = 7.6 Hz), 1.51 1.70 (m, 2H), 1.88 2.00 (m, 1H), 2.07 2.20 (m, 1H), 2.26 2.38 (m, 1H), 2.52 2.60 (m, 1H), 2.65 2.88 (m, 2H), 2.94 (d, 1H, J = 17.2 Hz), 3.27 (d, 1H, S28

J = 17.2 Hz), 3.62 (s, 3H), 3.83 (s, 3H), 5.24 (s, 1H), 6.97 (d, 1H, J = 7.6 Hz), 7.14 (dd, 1H, J = 7.6, 7.6 Hz), 7.23 (dd, 1H, J = 7.6 Hz), 7.84 (d, 1H, J = 7.6 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 13.7, 14.5, 14.7, 17.6, 23.5, 29.6, 39.1, 39.2, 51.3, 52.1, 52.4, 55.8, 69.4, 126.5, 126.5, 128.1, 128.3, 133.0, 136.9, 169.1, 169.7. Anal. Calcd for C 21 H 30 O 4 S 2 : C, 61.43; H, 7.36. Found: C, 61.19; H, 7.24. Dimethyl (4j). 1,3-bis(ethylthio)-3-phenyl-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate Yellow oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 47.1 mg (98%, d.r. = 1:1.4). * shows the peaks of minor diastereomer. IR (neat) 2951, 2927, 1735, 1625, 1491, 1435, 1373, 1258, 1219, 1098, 1067, 982, 767 cm 1. CO2 Me Ph 1 H NMR (400 MHz, CDCl 3 ) δ 0.88 1.41 (m, 6+6*H), 2.34* (s, 3H), 1.72 3.00 (m, 6+5*H), 3.24* (d, 1H, J = 17.6 Hz), 3.67* (s, 3H), 3.75 (s, 6H), 3.84* (s, 3H), 4.27 (s, 1H), 5.01* (s, 1H), 7.00 8.00 (m, 9H+9H*). 13 C NMR (100 MHz, CDCl 3 ) δ 13.2, 13.3, 14.4, 14.8, 22.8, 23.6, 26.3, 26.6, 30.0, 30.5, 37.4, 41.2, 51.0, 51.9, 52.1, 52.6, 56.8, 57.4, 69.5, 70.6, 126.5, 126.8, 127.4, 127.4, 128.2, 128.3, 128.3, 128.5, 128.5, 129.8, 130.2, 132.1, 134.8, 137.9, 138.1, 140.0, 140.6, 141.8, 142.5, 142.7, 167.6, 168.4, 168.8, 169.1. Anal. Calcd for C 24 H 28 O 4 S 2 : C, 64.83; H, 6.35. Found: C, 64.63; H, 6.15. CO2 Et CO 2 Et Diethyl 1,3-bis(ethylthio)-3-methyl-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4l). Yellow oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 33.3 mg (81%, d.r. = 1:1.2 with 20 mol% Sc(OTf) 3 ). * shows the peaks of minor diastereomer. IR (neat) 2975, 2928, 2870, 1758, 1732, 1451, 1376, 1365, 1297, 1264, 1234, 1216, S29

1190, 1095, 1044, 977, 864, 778 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 1.09 1.39 (m, 12+12*H), 1.77* (s, 3H), 1.83 (s, 3H), 2.45 3.05 (m, 5+5*H), 3.04 (d, 1H, J = 17.6 Hz), 3.36* (d, 1H, J = 17.6 Hz), 4.08 4.48 (m, 4+4*H), 4.52 (s, 1H), 5.04* (s, 1H), 6.93 (d, 1H, J = 8.0 Hz), 6.96* (d, 1H, J = 8.0 Hz). 7.08 7.26 (m, 2H+2H*), 7.64 (d, 1H, J = 8.0 Hz), 7.82* (d, 1H, J = 8.0 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 13.8, 13.8, 13.9, 14.0, 14.1, 14.4, 14.6, 22.8, 23.9, 25.1, 26.4, 29.6, 29.7, 32.5, 42.0, 43.7, 47.4, 50.3, 50.7, 51.2, 61.0, 61.2, 61.7, 61.8, 68.6, 68.7, 126.3, 126.4, 126.5, 126.8, 127.9, 128.0, 128.4, 128.5, 132.1, 133.3, 137.1, 138.9, 167.6, 168.0, 169.0, 169.9. Anal. Calcd for C 21 H 30 O 4 S 2 : C, 61.43; H, 7.36. Found: C, 61.71; H, 7.11. SPr CO2 Me SPr Dimethyl 3-methyl-1,3-bis(propylthio)-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4m). Colorless oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 34.2 mg (75%, d.r. = 1:1.4). * shows the peaks of minor diastereomer. IR (neat) 2959, 2931, 2871, 1763, 1736, 1454, 1432, 1378, 1354, 1266, 1235, 1218, 1043, 746 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 0.85 1.80 (m, 10H+10H*), 1.74* (s, 3H), 1.77 (s, 3H), 2.35 2.95 (m, 5+5*H), 3.07 (d, 1H, J = 17.6 Hz), 3.36 (d, 1H, J = 17.6 Hz), 3.67* (s, 3H), 3.74 (s, 3H), 3.74 (s, 3H), 3.84* (s, 3H), 4.50 (s, 1H), 5.09* (s, 1H), 6.94 (d, 1H, J = 7.6 Hz), 6.96* (d, 1H, J = 7.6 Hz), 7.11 (d, 1+1*H, J = 7.6 Hz), 7.23 (d, 1+1*H, J = 7.6 Hz), 7.66 (d, 1H, J = 7.6 Hz), 7.89* (d, 1H, J = 7.6 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 13.7, 13.7, 13.8, 13.9, 22.5, 23.0, 24.8, 26.5, 30.7, 31.7, 37.6, 40.4, 42.1, 43.7, 47.4, 50.2, 50.2, 51.4, 51.9, 52.1, 52.5, 52.7, 68.8, 69.0, 126.4, 126.5, 126.6, 126.8, 127.9, 128.1, 128.5, 128.6, 132.4, 133.3, 136.7, 138.4, 168.2, 168.6, 169.5, 170.1. Anal. Calcd for C 21 H 30 O 4 S 2 : C, 61.43; H, 7.36. Found: C, 61.62; H, 7.61. S30

Si-Pr CO2 Me Si-Pr Dimethyl 1,3-bis(isopropylthio)-3-methyl-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (4n). Yellow oil (purified by preparative TLC, Hexane/EtOAc = 5/1). Yield: 24.2 mg (58%, d.r. = 1:1.1). * shows the peaks of minor diastereomer. IR (neat) 2935, 2925, 2864, 1735, 1452, 1433, 1265, 1240, 1216, 1155, 1044 cm 1. 1 H NMR (400 MHz, CDCl 3 ) δ 1.15* (d, 1H, J = 6.8 Hz), 1.25 1.49 (m, 12H+9H*), 1.81 (s, 3+3*H), 2.80 3.46* (m, 4+4*H), 3.63* (s, 3H), 3.68 (s, 3H), 3.77 (s, 3H), 3.84* (s, 3H), 4.49 (s, 1H), 5.11* (s, 1H), 6.95 (d, 1+1*H, J = 7.6 Hz), 7.81 (d, 1+1*H, J = 7.6 Hz), 7.22 (d, 1+1*H, J = 7.6 Hz), 7.80 (d, 1H, J = 7.6 Hz), 7.84* (d, 1H, J = 7.6 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 23.0, 24.2, 24.4, 24.6, 25.2, 25.9, 26.2, 26.3, 27.0, 29.7, 33.7, 34.4, 38.3, 39.3, 42.5, 44.8, 49.1, 49.3, 49.8, 52.0, 52.1, 52.2, 52.4, 52.6, 69.6, 69.7, 126.4, 126.6, 126.6, 128.0, 128.4, 128.6, 128.7, 133.2, 133.3, 137.2, 137.5, 168.8, 168.9, 169.5, 170.0. Anal. Calcd for C 21 H 30 O 4 S 2 : C, 61.43; H, 7.36. Found: C, 61.56; H, 7.51. S31

3. DFT calculations All calculations were performed with the Gaussian 09 package. 6 The promising pathway was investigated using the Ti-catalyzed reaction model by M06/LANL2DZ for Ti, 6-31G* for the rest with the polarizable continuum model (PCM, ClCH2CH2Cl). 7,8 Frequency analyses were also carried out to identify the stationary points (RT, INT, PD: no imaginary frequency, TS: one imaginary frequency) and to estimate thermodynamic properties at 298.15 K and 1atm and Gibbs free energies. The molecular structures were depicted by using the CYLview v1.0.561 β. 9 After ring opening of cyclic thionium (TS2), the sequential C 1 -C 2 /C2-C3/C 4 -C 5 bond rotation would occur with lower energy barrier. At the C-C bond formation process (TS3), it should be possible to exist various diastereomeric TSs (TS3t, TS3c) leading to trans and cis adducts, respectively (Figure S1). Figure S1. The 3D structures and the relative Gibbs free energies in the pathways leading to (a) trans and (b) cis adducts S32

RT SCF Done: E(RM06) = -3656.64261087 a.u. Sum of electronic and thermal Free Energies= -3656.337238 a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-4.027737 0.426228-1.169102 2 6 0-4.288881 1.088304 0.202207 3 6 0-1.072966 0.126115-0.889755 4 6 0-1.931880-1.037934-0.967118 5 6 0-3.325480-0.900647-1.177879 6 1 0-5.003160 0.306278-1.664944 7 1 0-3.487110 1.165644-1.783145 8 6 0-1.348418-2.318805-0.998140 9 1 0-0.266753-2.415682-0.918217 10 6 0-4.075321-2.058340-1.387600 11 1 0-5.147529-1.968343-1.559132 12 6 0-3.489542-3.317739-1.402123 13 1 0-4.104152-4.197369-1.581543 14 6 0-2.115607-3.448899-1.212588 15 1 0-1.642589-4.427226-1.255220 16 16 0-2.694239 1.471224 1.067297 17 16 0-5.057301-0.065384 1.431165 18 6 0-2.246306 3.097462 0.393017 19 1 0-1.234993 3.295868 0.763920 20 1 0-2.218572 3.104256-0.703067 21 1 0-2.917349 3.881360 0.756216 22 6 0-6.662612-0.430862 0.661913 23 1 0-6.558808-0.850642-0.344592 24 1 0-7.128268-1.187488 1.301575 25 1 0-7.313035 0.449337 0.635804 26 1 0-1.365374 0.965351-1.523205 27 6 0 0.190863 0.228248-0.347024 28 6 0 1.074916 1.295675-0.791514 29 6 0 0.681802-0.597601 0.748386 30 8 0 0.495706 2.264462-1.463247 31 8 0 2.298319 1.323411-0.580199 32 8 0 1.876983-0.721117 1.063616 33 8 0-0.256165-1.162285 1.467131 34 6 0 1.342808 3.303372-1.985254 35 6 0 0.161234-2.021535 2.541296 36 1 0 2.079375 2.875519-2.670752 37 1 0 0.671687 3.980956-2.512301 38 1 0 1.850640 3.819410-1.166469 39 1 0 0.710400-1.444663 3.289793 40 1 0-0.761206-2.422582 2.960413 41 1 0 0.794162-2.824163 2.151845 42 22 0 3.648176-0.110431 0.136127 43 17 0 5.295976 0.813537-1.057149 44 17 0 3.858308 1.307768 1.917431 45 6 0-5.140301 2.332531 0.022680 46 1 0-6.117495 2.063931-0.399246 47 1 0-5.304268 2.840890 0.979995 48 1 0-4.676124 3.037414-0.679981 49 17 0 2.879078-1.400253-1.632633 50 17 0 4.744704-1.799947 1.102071 TS1 SCF Done: E(RM06) = -3656.64135241 a.u. Sum of electronic and thermal Free Energies= -3656.334499 a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0 4.205462-0.548670-1.029427 2 6 0 4.155942-1.102509 0.406422 3 6 0 1.217312-0.338121-0.899266 4 6 0 2.065300 0.838975-1.101763 5 6 0 3.463974 0.732367-1.265753 6 1 0 5.264082-0.406646-1.292720 7 1 0 3.849797-1.347643-1.702598 8 6 0 1.444217 2.082728-1.302169 9 1 0 0.360569 2.156405-1.228892 10 6 0 4.181785 1.871895-1.628969 11 1 0 5.258765 1.790462-1.776712 12 6 0 3.555251 3.096598-1.825274 13 1 0 4.142230 3.965251-2.116323 14 6 0 2.177775 3.201717-1.660143 15 1 0 1.671683 4.150053-1.826311 16 16 0 2.421932-1.591849 0.822395 17 16 0 4.423071 0.177976 1.719122 18 6 0 2.256861-3.211647 0.025133 19 1 0 1.189661-3.454774 0.053747 20 1 0 2.589924-3.191364-1.019127 21 1 0 2.810832-3.971005 0.584175 22 6 0 6.028870 0.879401 1.243199 23 1 0 5.957769 1.488897 0.336508 24 1 0 6.321659 1.526617 2.076038 25 1 0 6.795810 0.106482 1.126567 26 1 0 1.422281-1.165284-1.582253 27 6 0-0.111142-0.303967-0.422075 28 6 0-1.065546-1.266222-0.899687 29 6 0-0.527743 0.548008 0.661597 30 8 0-0.582487-2.210243-1.686291 31 8 0-2.283467-1.259302-0.626849 32 8 0-1.708565 0.721173 1.028766 33 8 0 0.452639 1.121921 1.326163 34 6 0-1.519740-3.151151-2.234426 35 6 0 0.098233 2.000573 2.404279 36 1 0-2.284330-2.626595-2.814300 37 1 0-0.927691-3.803185-2.876561 38 1 0-1.992766-3.723695-1.432131 39 1 0-0.427281 1.445082 3.185630 40 1 0 1.045090 2.390079 2.778544 41 1 0-0.536466 2.811310 2.035441 42 22 0-3.519600 0.163129 0.216187 43 17 0-5.276294-0.700698-0.887683 44 17 0-3.685471-1.284640 1.992247 45 6 0 5.112076-2.270099 0.569311 46 1 0 6.146516-1.918306 0.464672 47 1 0 5.007300-2.738031 1.554758 48 1 0 4.953043-3.030069-0.207522 49 17 0-2.868731 1.490706-1.582501 50 17 0-4.532187 1.861186 1.282568 INT1 SCF Done: E(RM06) = -3656.64878383 a.u. Sum of electronic and thermal Free Energies= -3656.343216 a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0 4.275127 0.621171 1.075930 2 6 0 4.202035 1.103640-0.374869 3 6 0 1.442219 0.491799 0.639033 4 6 0 2.171816-0.749782 1.065661 5 6 0 3.546283-0.659919 1.340996 6 1 0 5.341776 0.512160 1.318074 7 1 0 3.896107 1.433720 1.721162 8 6 0 1.503380-1.955028 1.279904 9 1 0 0.431434-2.020988 1.099203 10 6 0 4.225221-1.778072 1.819068 11 1 0 5.293623-1.703627 2.021437 12 6 0 3.554239-2.978300 2.027959 13 1 0 4.094538-3.845041 2.403093 14 6 0 2.191689-3.064525 1.757657 15 1 0 1.657265-3.997262 1.924877 16 16 0 2.381271 1.321976-0.839898 S33

17 16 0 4.963133-0.015128-1.617451 18 6 0 1.995130 3.040375-0.422070 19 1 0 0.905628 3.124670-0.495944 20 1 0 2.324295 3.293067 0.590947 21 1 0 2.455485 3.695933-1.164953 22 6 0 3.934571-1.515105-1.686312 23 1 0 2.871781-1.272996-1.799287 24 1 0 4.266450-2.031585-2.593216 25 1 0 4.083138-2.167787-0.822159 26 1 0 1.565775 1.259096 1.414692 27 6 0 0.007834 0.419336 0.272933 28 6 0-0.942949 1.185214 0.993506 29 6 0-0.463680-0.374486-0.799280 30 8 0-0.455228 2.027849 1.894624 31 8 0-2.189275 1.128048 0.839092 32 8 0-1.667611-0.523033-1.129432 33 8 0 0.469482-0.980869-1.522905 34 6 0-1.399570 2.783566 2.665479 35 6 0 0.019837-1.815586-2.600992 36 1 0-2.081066 2.112956 3.196762 37 1 0-0.799790 3.358849 3.371271 38 1 0-1.972587 3.450817 2.015446 39 1 0-0.503021-1.216638-3.351547 40 1 0 0.924528-2.254497-3.024232 41 1 0-0.645510-2.597221-2.222882 42 22 0-3.409272-0.123650-0.181730 43 17 0-5.146504 0.512505 1.120743 44 17 0-3.701777 1.601631-1.695264 45 6 0 4.945011 2.419200-0.553624 46 1 0 4.830741 2.827501-1.564058 47 1 0 4.627141 3.168173 0.180245 48 1 0 6.013377 2.231981-0.384892 49 17 0-2.710994-1.758279 1.343027 50 17 0-4.475763-1.638652-1.484701 TS2 SCF Done: E(RM06) = -3656.61854466 a.u. Sum of electronic and thermal Free Energies= -3656.317777 a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-4.332498-0.870497 0.887169 2 6 0-5.530572-0.702689 0.039568 3 6 0-1.343123-0.720908 0.219021 4 6 0-2.120116 0.439016 0.835717 5 6 0-3.483750 0.339517 1.172930 6 1 0-4.656798-1.354784 1.821618 7 1 0-3.766029-1.650555 0.335754 8 6 0-1.454831 1.617664 1.190063 9 1 0-0.390476 1.711063 0.988910 10 6 0-4.120960 1.387242 1.843476 11 1 0-5.172176 1.275546 2.117207 12 6 0-3.446997 2.557772 2.163330 13 1 0-3.962656 3.366243 2.677012 14 6 0-2.102698 2.667921 1.829211 15 1 0-1.544143 3.567423 2.080031 16 16 0-2.102416-1.312025-1.393623 17 16 0-5.804312 0.333867-1.236723 18 6 0-1.245717-2.906462-1.515132 19 1 0-0.164122-2.758898-1.613503 20 1 0-1.458626-3.534976-0.642539 21 1 0-1.619102-3.402872-2.415738 22 6 0-4.425604 1.490268-1.478822 23 1 0-3.487575 0.964472-1.675937 24 1 0-4.721966 2.052858-2.369272 25 1 0-4.330449 2.165160-0.623818 26 1 0-1.471683-1.579744 0.892242 27 6 0 0.134110-0.517532 0.052462 28 6 0 1.047739-1.306795 0.780881 29 6 0 0.674992 0.387152-0.883454 30 8 0 0.531254-2.244129 1.568580 31 8 0 2.308012-1.193821 0.748413 32 8 0 1.908974 0.531986-1.132804 33 8 0-0.182411 1.139198-1.557192 34 6 0 1.445119-3.026185 2.344253 35 6 0 0.370787 2.122236-2.439246 36 1 0 2.062511-2.381526 2.977094 37 1 0 0.820080-3.677133 2.956974 38 1 0 2.089861-3.621713 1.690956 39 1 0 0.925328 1.642630-3.251067 40 1 0-0.486027 2.669681-2.834361 41 1 0 1.037406 2.796039-1.889354 42 22 0 3.540737 0.140743-0.076659 43 17 0 5.183706-0.475649 1.384048 44 17 0 4.119128-1.466333-1.643017 45 6 0-6.649746-1.644966 0.285554 46 1 0-7.433796-1.615215-0.475997 47 1 0-6.250454-2.665226 0.367521 48 1 0-7.092125-1.405627 1.264027 49 17 0 2.654681 1.695899 1.472714 50 17 0 4.669603 1.790138-1.189251 INT2(INT2t) SCF Done: E(RM06) = -3656.63388316 a.u. Sum of electronic and thermal Free Energies= -3656.328842 a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-3.181959-0.421985-0.027370 2 6 0-3.416260 0.881630-0.499252 3 6 0-2.587085 2.045637-0.027781 4 6 0-0.680312-0.405796 0.493819 5 6 0-2.080495-0.649358 0.997738 6 1 0-3.150198 2.985202-0.185406 7 1 0-2.409941 2.011678 1.056808 8 6 0-4.428738 1.116053-1.431106 9 1 0-4.595831 2.133677-1.787118 10 6 0-3.986034-1.452993-0.510134 11 1 0-3.798577-2.467179-0.159697 12 6 0-5.220185 0.077056-1.903645 13 1 0-6.007737 0.274957-2.627775 14 6 0-4.993659-1.213237-1.437574 15 1 0-5.602983-2.040865-1.795901 16 6 0 0.252600 0.283257 1.297609 17 6 0-0.174820-1.037485-0.670259 18 8 0-0.209658 0.808657 2.432654 19 8 0-1.049208-1.731086-1.380069 20 8 0 1.013509-0.972533-1.088362 21 8 0 1.464363 0.487219 1.015031 22 6 0-0.571885-2.379276-2.565569 23 1 0 0.225933-3.085894-2.318986 24 1 0-1.437971-2.901204-2.973903 25 1 0-0.198320-1.638223-3.279691 26 6 0 0.773543 1.324937 3.343987 27 1 0 0.212423 1.638972 4.225127 28 1 0 1.491210 0.540287 3.603339 29 1 0 1.308391 2.172834 2.903461 30 22 0 2.751196-0.382762-0.265304 31 17 0 2.581801 1.532127-1.608641 32 17 0 3.919748-1.514831-1.844717 33 17 0 2.566934-2.253189 1.105278 34 17 0 4.482699 0.478627 0.922602 35 1 0-2.249562 0.061622 1.818450 36 16 0-2.084441-2.291027 1.844361 37 6 0-3.613911-2.137428 2.814141 38 1 0-3.676591-3.020933 3.456999 39 1 0-3.583093-1.242858 3.447335 40 1 0-4.500149-2.103068 2.170088 41 6 0-1.293493 2.249026-0.742389 42 6 0-1.091519 1.712417-2.106508 43 16 0-0.093415 3.273130-0.185239 44 1 0-0.041780 1.733467-2.423115 45 1 0-1.673434 2.350593-2.793091 46 1 0-1.512225 0.704254-2.202677 47 6 0-0.726869 3.927985 1.385642 48 1 0-1.638328 4.510317 1.223020 49 1 0 0.061737 4.585000 1.762375 50 1 0-0.899243 3.117313 2.102116 S34

TS3(TS3t) SCF Done: E(RM06) = -3656.63084420 a.u. Sum of electronic and thermal Free Energies= -3656.323067 a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-3.209972-0.479491 0.029581 2 6 0-3.496247 0.696467-0.678527 3 6 0-2.687666 1.932917-0.412053 4 6 0-0.732570-0.060279 0.385312 5 6 0-2.062752-0.421652 1.018494 6 1 0-3.138783 2.791234-0.942096 7 1 0-2.715099 2.201168 0.653549 8 6 0-4.523701 0.713514-1.619217 9 1 0-4.727044 1.633022-2.169453 10 6 0-3.979976-1.613680-0.209872 11 1 0-3.746894-2.534266 0.323775 12 6 0-5.286777-0.425506-1.853262 13 1 0-6.090159-0.402750-2.586809 14 6 0-5.013604-1.588732-1.141547 15 1 0-5.602040-2.487569-1.316477 16 6 0 0.250855 0.581318 1.227434 17 6 0-0.186426-0.911673-0.641280 18 8 0-0.244812 1.205737 2.280830 19 8 0-1.017039-1.785205-1.164878 20 8 0 0.977586-0.835808-1.094892 21 8 0 1.476588 0.638536 1.013080 22 6 0-0.501448-2.639046-2.199837 23 1 0 0.365504-3.196228-1.831021 24 1 0-1.321631-3.312611-2.447637 25 1 0-0.213833-2.041304-3.070675 26 6 0 0.697593 1.808066 3.185143 27 1 0 0.092099 2.253205 3.974843 28 1 0 1.363914 1.042672 3.592481 29 1 0 1.289061 2.571753 2.671387 30 22 0 2.775009-0.388518-0.244186 31 17 0 2.737822 1.500333-1.574596 32 17 0 3.864498-1.627790-1.768092 33 17 0 2.322814-2.203744 1.129557 34 17 0 4.511261 0.314753 0.993374 35 1 0-2.289621 0.378340 1.738908 36 16 0-1.816423-1.915957 2.074723 37 6 0-3.229406-1.710776 3.198905 38 1 0-3.187184-2.530547 3.922456 39 1 0-3.162527-0.758641 3.737942 40 1 0-4.180260-1.764280 2.656200 41 6 0-1.267499 1.879131-0.893138 42 6 0-1.002027 1.324184-2.254585 43 16 0-0.178169 3.146107-0.474113 44 1 0 0.070169 1.217237-2.462614 45 1 0-1.414660 2.041384-2.981334 46 1 0-1.516699 0.370748-2.415428 47 6 0-1.018298 4.083633 0.838022 48 1 0-1.933270 4.553045 0.465432 49 1 0-0.306532 4.863809 1.123758 50 1 0-1.229002 3.458726 1.710472 PD(PDt) SCF Done: E(RM06) = -3656.65445185 a.u. Sum of electronic and thermal Free Energies= -3656.344276a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-3.258577-0.561900 0.146755 2 6 0-3.655137 0.479569-0.700424 3 6 0-2.825085 1.724115-0.671942 4 6 0-0.845292 0.260655 0.109804 5 6 0-2.030200-0.274109 0.971672 6 1 0-3.154265 2.441557-1.436440 7 1 0-2.953421 2.222158 0.300823 8 6 0-4.775624 0.327842-1.511649 9 1 0-5.068357 1.140055-2.177357 10 6 0-4.001294-1.736206 0.192611 11 1 0-3.686067-2.547826 0.847094 12 6 0-5.519594-0.847658-1.461524 13 1 0-6.399449-0.961429-2.091970 14 6 0-5.133503-1.875436-0.605854 15 1 0-5.711962-2.796596-0.564227 16 6 0 0.211274 0.846702 1.048037 17 6 0-0.207578-0.865749-0.695265 18 8 0-0.309353 1.556387 2.014944 19 8 0-1.015010-1.845564-0.979958 20 8 0 0.952417-0.862813-1.104106 21 8 0 1.426949 0.685320 0.961959 22 6 0-0.469149-2.931205-1.761376 23 1 0 0.391763-3.360161-1.239820 24 1 0-1.280002-3.652883-1.849199 25 1 0-0.166494-2.554744-2.742850 26 6 0 0.616662 2.225600 2.894507 27 1 0-0.004179 2.796929 3.584341 28 1 0 1.218887 1.485086 3.426797 29 1 0 1.260794 2.884879 2.303499 30 22 0 2.820521-0.364003-0.240505 31 17 0 2.713229 1.448735-1.613615 32 17 0 3.885552-1.660582-1.703397 33 17 0 2.296942-2.105734 1.177039 34 17 0 4.518291 0.382145 0.979064 35 1 0-2.271416 0.549493 1.657328 36 16 0-1.433233-1.617204 2.076505 37 6 0-2.319517-1.120372 3.583500 38 1 0-2.108398-1.875077 4.346758 39 1 0-1.970129-0.143098 3.936273 40 1 0-3.400052-1.092874 3.402786 41 6 0-1.339569 1.418922-0.916107 42 6 0-1.151307 0.997998-2.374916 43 16 0-0.321153 2.976482-0.770246 44 1 0-0.092839 0.863456-2.630698 45 1 0-1.555808 1.782203-3.024587 46 1 0-1.695495 0.069674-2.595790 47 6 0-1.236533 4.054151 0.372720 48 1 0-2.188364 4.392009-0.048417 49 1 0-0.587443 4.926679 0.505378 50 1 0-1.396712 3.588404 1.350706 INT2c SCF Done: E(RM06) = -3656.63681313 a.u. Sum of electronic and thermal Free Energies= -3656.330651 a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-3.154393-0.485031-0.072336 2 6 0-3.482246 0.676348 0.652114 3 6 0-2.600939 1.170200 1.765394 4 6 0-0.616196-0.694676 0.274085 5 6 0-1.976091-1.332791 0.386081 6 1 0-3.178388 1.813455 2.457213 7 1 0-2.210484 0.368785 2.408636 8 6 0-4.604504 1.428421 0.301049 9 1 0-4.844996 2.321503 0.880083 10 6 0-3.963381-0.836578-1.150886 11 1 0-3.705435-1.721463-1.731450 12 6 0-5.404902 1.058712-0.772616 13 1 0-6.278036 1.652583-1.034670 14 6 0-5.073165-0.075547-1.503981 15 1 0-5.682313-0.376432-2.354395 16 6 0 0.328444-0.856194 1.317072 S35

17 6 0-0.144327-0.121846-0.925008 18 8 0-0.129916-1.380381 2.447116 19 8 0-0.991597-0.076799-1.938342 20 8 0 1.007512 0.384057-1.088103 21 8 0 1.546516-0.525844 1.268351 22 6 0-0.490494 0.433672-3.180861 23 1 0 0.388232-0.138357-3.497644 24 1 0-1.307022 0.311988-3.893067 25 1 0-0.222663 1.490611-3.081557 26 6 0 0.821791-1.606624 3.495591 27 1 0 0.267813-2.118110 4.283195 28 1 0 1.644525-2.230778 3.134958 29 1 0 1.218337-0.654438 3.861683 30 22 0 2.775516-0.095241-0.279222 31 17 0 2.916921 2.087002 0.603496 32 17 0 3.827561 0.525781-2.190098 33 17 0 2.368162-2.247499-1.048163 34 17 0 4.568456-0.781086 0.932053 35 1 0-2.139443-1.543040 1.452278 36 16 0-1.845641-3.015225-0.367967 37 6 0-3.301030-3.805541 0.380397 38 1 0-3.286434-4.857939 0.080494 39 1 0-3.251795-3.750245 1.474138 40 1 0-4.234348-3.350292 0.030076 41 6 0-1.455248 2.028717 1.344135 42 6 0-0.341804 2.260287 2.282022 43 16 0-1.601083 2.819799-0.123789 44 1 0-0.304575 3.320261 2.574538 45 1 0 0.632767 2.048039 1.808943 46 1 0-0.451827 1.652314 3.185113 47 6 0-0.122055 3.861835-0.223349 48 1 0-0.115873 4.604748 0.579955 49 1 0-0.194904 4.370158-1.188581 50 1 0 0.787510 3.248951-0.198421 TS3c SCF Done: E(RM06) = -3656.63266160 a.u. Sum of electronic and thermal Free Energies= -3656.323752 a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0 3.201543 0.490994-0.102704 2 6 0 3.577539-0.619359 0.668398 3 6 0 2.679693-1.061485 1.787906 4 6 0 1.376160-1.649736 1.318027 5 6 0 0.686980 0.431064 0.375467 6 6 0 1.964543 1.249232 0.337843 7 1 0 3.167216-1.854365 2.380590 8 1 0 2.459801-0.251620 2.498300 9 6 0 4.732885-1.331361 0.353848 10 1 0 5.006876-2.195531 0.960273 11 6 0 3.994625 0.856912-1.185277 12 1 0 3.694091 1.704967-1.799799 13 6 0 5.523563-0.952615-0.726217 14 1 0 6.424476-1.513669-0.966523 15 6 0 5.147545 0.141144-1.497517 16 1 0 5.752064 0.441591-2.351471 17 6 0-0.309325 0.815094 1.350644 18 6 0 0.166373-0.141896-0.835258 19 8 0 0.170523 1.417362 2.423243 20 8 0 1.000631-0.196097-1.844944 21 8 0-0.972934-0.657503-0.949480 22 8 0-1.534611 0.585249 1.281561 23 6 0 0.512188-0.785415-3.062669 24 1 0 1.328415-0.685411-3.777514 25 1 0 0.268947-1.839175-2.895446 26 1 0-0.376946-0.247299-3.406410 27 6 0-0.777853 1.820265 3.425571 28 1 0-0.189076 2.321500 4.193452 29 1 0-1.514731 2.502376 2.993028 30 1 0-1.285047 0.942175 3.837267 31 6 0 0.308508-1.856631 2.332432 32 1 0-0.697153-1.934435 1.901308 33 1 0 0.517295-2.804117 2.854414 34 1 0 0.328445-1.061782 3.086007 35 16 0 1.564319-2.759154 0.013202 36 6 0 0.016983-3.711650-0.010393 37 1 0-0.839465-3.076276-0.258051 38 1 0 0.157911-4.453618-0.801934 39 1 0-0.144546-4.227571 0.940883 40 22 0-2.787167 0.059152-0.294840 41 17 0-3.059405-1.969806 0.787437 42 17 0-3.791476-0.653033-2.169922 43 17 0-2.102598 2.055914-1.248318 44 17 0-4.523977 1.009314 0.760771 45 1 0 2.146030 1.579597 1.370025 46 16 0 1.615568 2.827763-0.556452 47 6 0 2.938800 3.854792 0.149287 48 1 0 3.930607 3.466296-0.108710 49 1 0 2.828509 4.855996-0.278816 50 1 0 2.839166 3.922506 1.238783 PDc SCF Done: E(RM06) = -3656.65261705 a.u. Sum of electronic and thermal Free Energies= -3656.344328 a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-3.251886-0.641685-0.134087 2 6 0-3.697267 0.488749 0.560246 3 6 0-2.786694 1.040844 1.608397 4 6 0-0.800821-0.119679 0.449028 5 6 0-1.932840-1.193566 0.336710 6 1 0-3.160735 2.001675 1.989655 7 1 0-2.738721 0.363884 2.481179 8 6 0-4.925177 1.059465 0.240219 9 1 0-5.255734 1.950447 0.774780 10 6 0-4.045142-1.200683-1.129997 11 1 0-3.693235-2.076898-1.672844 12 6 0-5.721673 0.495149-0.751615 13 1 0-6.684332 0.941003-0.995235 14 6 0-5.280986-0.635424-1.433648 15 1 0-5.899263-1.078711-2.212175 16 6 0 0.291853-0.668988 1.364696 17 6 0-0.201830 0.129135-0.938412 18 8 0-0.167362-1.360969 2.374184 19 8 0-1.111340 0.130892-1.872692 20 8 0 0.988859 0.277156-1.208732 21 8 0 1.494183-0.449922 1.248057 22 6 0-0.677591 0.443773-3.210766 23 1 0 0.057746-0.293569-3.543365 24 1 0-1.579972 0.403943-3.819232 25 1 0-0.240845 1.447234-3.218151 26 6 0 0.810523-1.893151 3.293371 27 1 0 0.237032-2.472371 4.015661 28 1 0 1.516085-2.526859 2.748489 29 1 0 1.341351-1.069928 3.780614 30 22 0 2.872067 0.059877-0.301941 31 17 0 2.539176 2.232849 0.331558 32 17 0 3.941994 0.578183-2.178037 33 17 0 2.608811-2.151012-0.844787 34 17 0 4.575365-0.279777 1.088164 35 1 0-2.086047-1.548368 1.363890 36 16 0-1.270917-2.659445-0.555305 37 6 0-1.979007-3.955456 0.503594 38 1 0-1.702889-4.918096 0.063591 39 1 0-1.573083-3.894871 1.519834 40 1 0-3.071728-3.875680 0.526995 41 6 0-1.351768 1.256159 1.098195 42 6 0-0.486182 1.737511 2.256822 43 1 0-0.455480 0.986494 3.057082 44 1 0 0.536927 1.978489 1.947463 45 1 0-0.929630 2.633996 2.702681 46 16 0-1.384245 2.557973-0.256878 47 6 0-1.234524 4.115913 0.658628 48 1 0-0.253910 4.231940 1.130600 49 1 0-1.351761 4.893428-0.103556 50 1 0-2.034185 4.239294 1.397585 S36