Supporting Information

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1 Supporting Information Radical Cyclizations terminated by Ir-catalyzed AT Andreas Gansäuer,* Matthias Otte, Lei Shi Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard Domagk Strasse 1, Bonn, Germany General Information All the reactions involving air- or moisture sensitive compounds (except the reactions using Vaska`s complex IrCl(CO)(PPh 3 ) 2 (1)) were carried out under argon using standard Schlenk and vacuum line technique. All reactions using Vaska`s complex were carried out in vessels from Kimble & Contess. Those were stored at 120 C and were flushed four times with hydrogen before chemicals were added. The hydrogen source was a hydrogen generator GE GC 300 from Proton Energies Inc.. All solvent were dried and deoxygenated according to standard procedure (TF over K, C 2 Cl 2 over Ca 2 ) before use. All chemical were purchased from Alfa Aesar, Fluka, Acros and Aldrich without purification before use. 1 MR and 13 C MR spectra were measured on Bruker AMX 300 Mz or Bruker 400 Mz spectrometer. 1 MR chemical shift were given in ppm, and calibrated by using the residual undertreated solvent as internal reference (CCl 3 (7.26 ppm), d 5 benzene (7.16ppm)). 13 C MR chemical shift were recorded in ppm from the solvent peak employed as internal reference (CDCl 3 (77.0 ppm), C 6 D 6 (128.0 ppm). IR spectra were measured on a ATR-IR-Spectrometor icolettm 380 instrument as neat film. ighresolution mass spectra analysis data were obtained on a Thermoquest MAT 95 XL instrument. igh pressure liquid chromatography (PLC) was performed on KAUER instrument using chiral column as noted for each compound. SiO 2 chromatography was carried out with silica gel ( mesh) supplied by Merck and Macherey-agel in solvent mixtures of ethyl acetate (EA) in cyclohexane (C). For measuring the melting points, small samples of the compounds were crystallized from the solvent mixture used for chromatography. This is indicated in brackets after the melting point. S1

2 Experiments 1. General procedures 1.1. (GP1) General procedures for radical cyclizations terminated by Ir-catalyzed AT A mixture of titanocene catalyst (0.15 mmol), dry 2,4,6-Me 3 Py*Cl (1.50 mmol), Vaska`s complex IrCl(CO)(PPh 3 ) 2 (1) (0.05 mmol) and Mn (3.00 mmol) dust was placed under an atmosphere of hydrogen gas. Then, a solution of epoxide (1.00 mmol) in dry TF (5.0 ml) was added. The mixture was stirred under hydrogen atmosphere (4bar) at room temperature, filtered, diluted with C 2 Cl 2 (30 ml) and washed with phosphate buffer (20 ml). The phases where separated and the aqueous solution was washed C 2 Cl 2 (3 x 30 ml). the combined organic layers where dried (MgSO 4 ) The volatiles were removed under reduced pressure and the crude product was purified by SiO 2 chromatography (GP2) General procedure of the Sonogashira coupling reaction To a dried schlenk flask was added Pd(PPh 3 ) 2 Cl 2 (0.2 mmol), CuI (0.2 mmol), iodoarene (11.0 mmol), alkyne and freshly distilled Et 3 under argon. The resulting mixture was stirred for 16 h at 50 C. 50 ml of MTBE were added and the mixture filtered. After removal of solvent using rotary evaporator, the crude compound was purified by distillation or SiO 2 chromatography (GP3) General procedure of mcpba epoxidation A solution of olefin (10.0 mmol) in C 2 Cl 2 (150 ml) was cooled to 0 o C, and then mcpba (12.0 mmol) (70%~75%), was added into this solution. The resulting mixture was allowed to warm to room temperature and stirred over night. The reaction mixture was diluted with 50 ml C 2 Cl 2 and washed two times with 25% aqueous K 2 CO 3 solution and dried over MgSO 4. After removal of solvent using rotary evaporator, the crude product was purified by SiO 2 chromatography. 1. Synthesis of epoxides Epoxides 2, 14 and 18 were prepared according to literature procedures. S1 S2

3 Methyl--(2-methyl-allyl)--prop-2-ynyl-benzene-sulfonamide (S2) S2 To a solution of S1 S3 (5.23 g, 25.0 mmol) and aceton (150 ml) at 0 C K 2 CO 3 (5.25 g, 38.0 mmol) and 3- Bromo-2-methyl-propene (5.40 g, 40.0 mmol) were added. The resulting mixture was heated under reflux for 5 h. Stirring was continued at room temperature for 16 h. The solvent was removed under reduced pressure and the resulting solid was solved in ethyl acetate, washed with water and brine and dried over MgSO 4. The solvent was removed under reduced pressure and the crude product was purified by SiO 2 chromatography (19% EA in C, R f = 0.54 ) to give S2 (6.37g, 24.2 mmol, 97%) as a colorless solid. 1 - MR (300 Mz, CDCl 3 ): δ 7.67 (d, J = 8.12 z, 2), 7.22 (d, J = 7.93 z, 2), (m, 2), 3.92 (d, J = 2.45 z, 2), 3.66(s, 2), 2.35 (s, 3), 1.89 (t, J = 2.54 z, 1), 1.69 (s, 3); 13 C-MR (75 Mz, CDCl 3 ): δ , , , , , , 76.50, 73.84, 52.53, 35.58, 21.68, 19.80; m.p.: C (19% EA, 81% C). 1 -MR data in agreement with published data. S Methyl--(2-methyl-oxiranyl-methyl)--prop-2-ynyl-benzene-sulfonamide (6) S4 According to GP3, S2 (2.63 g, 10.0 mmol) was treated with mcpba (2.96 g, 12.0 mmol) in C 2 Cl 2 (150 ml). The crude product was purified by SiO 2 chromatography (19% EA in C, R f = 0.25 ) to give 6 (1.88 g, 6.74 mmol, 67%) as a colorless oil. 1 -MR (400 Mz, C 6 D 6 ): δ 7.71 (d, J = 8.18 z, 2), 6.82 (d, J = 7.93 z, 2), (m, 2), 3.28 (d, J = z, 1), 3.17 (d, J = z, 1), 2.38 (d, J = 4.78 z, 1), 2.12 (d, J = 4.78 z, 1), 1.92(s, 3), (m, 1), 1.16 (s, 3); 13 C-MR (100 Mz,, C 6 D 6 ): δ , , , , 77.12, 73.99, 55.24, 51.41, 51.09, 37.67, 21.17, 18.74; IR (neat): 3270, 2935, 1595, 1495, 1435, 1400, 1345, 1330, 1185, 1160, 1100, 1090, 935, 900, 810, 750, 655, 565, 540, 435, 405 cm -1 ; 1 -MR and 13 C-MR data in agreement with published data. S4 S3

4 2.3. -(but-2-ynyl)-4-methyl--(2-methyl-allyl)-benzene-sulfonamide (S3) S5 S2 (1.32 g, 5.00 mmol) was solved in TF (50.0 ml) and cooled to -78 C. n-buli (3.50 ml, 5.60 mmol) (1.60 M in hexane) was added drop wise. The mixture was stirred for 10 minutes at room temperature before cooling down to -78 C. MeI (3.55 g, 25.0 mmol) was added and the mixture stirred over night at room temperature. The reaction was finished by adding 100 ml saturated aco 3 solution. The mixture was diluted with ether and the phases were separated. The aqueous layer was extracted with ether (2x100 ml). The combined organic phases were washed with brine and dried over MgSO 4. The solvent was removed under reduced pressure and the crude product was purified by SiO 2 chromatography (15% EA in C, R f = 0.53 ) to give S3 (1.19 g, 4.33 mmol, 87%) as a pale yellow solid (87%). 1 -MR (400 Mz, CDCl 3 ): δ 7.74 (d, J = 8.30 z, 2), 7.29 (d, J = 7.93 z, 2), 4.94 (d, J = 1.07 z, 2), 3.97 (q, J = 2.31 z, 3), 3.69 (s, 2), 2.42 (s, 3), 1.75 (s, 3), 1.50 (s, J = 2.39 z, 3); 13 C-MR (100 Mz, CDCl 3 ): δ , , , , , , 81.61, 71.66, 52.55, 36.16, 21.63, 19.86, 3.31; IR (neat): 3075, 2975, 2915, 1595, 1440, 1360, 1340, 1330, 1155, 1120, 1015, 915, 900, 845, 815, 800, 760, 710, 655, 595, 540, 500, 410 cm -1 ; RMS (ESI positive): calcd. for C O 2 Sa [M + a] + = , found m.p.: C (15% EA, 85% C). 1 -MR and 13 C-MR data in agreement with published data. S (but-2-ynyl)-4-methyl--((2-methyl-oxiran-2-yl)-methyl)-benzene-sulfonamide (4) According to GP3, S3 (1.06 g, 3.82 mmol) was treated with mcpba (1.26 g, 5.12 mmol) in C 2 Cl 2 (60 ml). The crude product was purified by SiO 2 chromatography (6% EA in C, R f = 0.19 (13%EA in C)) to give 4 (944 mg, 3.22 mmol, 84%) as a colorless oil. 1 -MR (300 Mz, CDCl 3 ): δ 7.69 (d, J = 8.31 z, 2), 7.25 (d, J = 8.50 z, 2), (m, 2), 3.26 (dd, J = z, J = 5.10 z, 2), 2.73 (d, J = 4.72 z, 1), ), 2.60 (d, J = 4.72 z, 1), 2.38 (s, 3), 1.50 (t, J = 2.36 z, 3) 1.37 (s, 3); 13 C-MR (75 Mz, CDCl 3 ): δ , , , , 81.92, 71.62, 55.69, 51.75, 51.02, 38.33, 21.59, 18.97, 3.31; IR (neat): 2920, 1705, 1440, 1395, 1330, 1160, 1100, 1040, 1010, 925, 810, 745, 655, 560, 540, 455, 410 cm -1 ; RMS (ESI positive): calcd. for C O 3 Sa [M + a] + = , found S4

5 Methyl--(2-methyl-allyl)--(3-phenylprop-2-ynyl)-benzene-sulfonamide (S4) According to GP2, S2 (2.63 g, 10.0 mmol) was treated with iodobenzene (2.24 g, 11.0 mmol), CuI (38.0 mg, 0.2 mmol), Pd(PPh 3 ) 2 Cl 2 (140 mg, 0.2 mmol) in Et 3 (90.0 ml) at 50 C for 16 h. The crude product was purified by SiO 2 chromatography (4% EA in C, R f = 0.33 (8% EA in C) ) to give S4 (2.98 g, 8.79 mmol, 88%) as a colorless solid. 1 -MR (400 Mz, CDCl 3 ): δ 7.70 (d, J = 8.31 z, 2), (m, 5), (m, 2), (m, 2), 4.18 (s, 2), 3.72 (s, 2), 2.25 (s, 3), 1.73 (s, 3); 13 C-MR (100 Mz, CDCl 3 ): δ , , , , , , , , , , 85.81, 81.74, 52.86, 36.54, 21.54, 19.90; IR (neat): 2915, 2360, 2340, 1655, 1435, 1345, 1325, 1305, 1245, 1185, 1165, 1090, 1030, 960, 900, 800, 750, 660, 570, 500, 450, 405 cm -1 ; m.p.: 66 C (8% EA, 92% C) Methyl--((2-methyl-oxiran-2-yl)-methyl)--(3-phenyl-prop-2-ynyl)-benzene-sulfonamide (8) S4 mcpbs C 2 Cl 2,0 Ctort,16h O 8 According to GP3, S4 (678 mg, 2.00 mmol) was treated with mcpba (640 mg, 2.60 mmol) in C 2 Cl 2 (30.0 ml). The crude product was purified by SiO 2 chromatography (13% EA in C, R f = 0.13) to give 8 (429 mg, 1.21 mmol, 61%) as a colorless solid. 1 -MR (300 Mz, C 6 D 6 ): δ (m, 2), (m, 5), 6.74 (d, J = 7.93 z, 2), 4.48 (d, J = z, 1), 4.38 (d, J = z, 1), 3.41 (d, J = z, 1), 3.28 (d, J = z, 1), 2.42 (d, J = 4.72 z, 1), 2.14 (d, J = z, 1), 1.84 (s, 3), 1.22 (s, 3); 13 C-MR (75 Mz, C 6 D 6 ): δ , , , , , , , , 85.91, 82.91, 55.37, 51.72, 51.12, 38.65, 21.06, 18.82; IR (neat): 2360, 2340, 1490, 1445, 1345, 1305, 1160, 1145, 1100, 1040, 960, 940, 900, 875, 815, 765, 660, 570, 545, 480, 440 cm -1 ; RMS (ESI positive): calcd. for C O 3 Sa [M + a] + = , found m.p.: 108 C (13% EA, 87% C). S5

6 2.7. -(3-(4-Bromo-phenyl)-prop-2-ynyl)-4-methyl--(2-methyl-allyl)-benzene-sulfonamide (S5) According to GP2, S2 (1.32 g, 5.00 mmol) was treated with 1-bromo-4-iodobenzene (1.56 g, 5.50 mmol), CuI (19.0 mg, 0.1 mmol), Pd(PPh 3 ) 2 Cl 2 (70.0 mg, 0.1 mmol) in Et 3 (50.0 ml) at 50 C for 16 h. The crude product was purified by SiO 2 chromatography (6% EA in C, R f = 0.56 (13% EA in C) ) to give S5 (1.93 g, 4.61 mmol, 92%) as a pale brown solid. 1 -MR (300 Mz, CDCl 3 ): δ 7.67 (dt, J = 8.31 z, J = 1.89 z, 2), 7.27 (dt, J = 8.69 z, J = 2.08 z, 2), 7.14 (d, J = 8.31 z, 2), 6.89 (dt, J = 8.69 z, J = 1.89 z, 2), (m, 2), 4.13 (s, 2), 3.68 (s, 2), 2.24 (s, 3), 1.70 (s, 3); 13 C-MR (75 Mz, CDCl 3 ): δ , , , , , , , , , , 84.74, 83.14, 52.98, 36.52, 21.61, 19.91; IR (neat): 3735, 2915, 2360, 2345, 1660, 1595, 1485, 1470, 1345, 1325, 1285, 11560, 1120, 1070, 955, 915, 770, 660, 635, 575, 545, 445, 430 cm -1 ; RMS (ESI positive): calcd. for C BrO 2 Sa [M + a] + = , found m.p.: C (6% EA, 94% C) (3-(4-Bromo-phenyl)-prop-2-ynyl)-4-methyl--((2-methyl-oxiran-2-yl)-methyl)-benzenesulfonamide (10) According to GP3, S5 (1.40 g, 3.35 mmol) was treated with mcpba (1.11 g, 4.52 mmol) in C 2 Cl 2 (60.0 ml). The crude product was purified by SiO 2 chromatography (20% EA in C, R f = 0.41) to give 10 (1.00 g, 2.30 mmol, 58%) as a colorless solid. 1 -MR (300 Mz, CDCl 3 ): δ 7.75 (dt, J = 8.31 z, J = 1.89 z, 2), 7.36 (dt, J = 8.50 z, J = 1.89 z, 2), 7.24 (d, J = 7.93 z, 2), 6.88 (dt, J = 8.69 z, J = 2.08 z, 2), 4.46 (d, J = z, 1), 4.36 (d, J = z, 1), 3.45 (d, J = z, 1), 3.32 (d, J = z, 1), 2.80 (d, J = 4.72 z, 1), 2.66 (d, J = 4.72 z, 1), 2.34 (s, 3), 1.44 (s, 3); 13 C-MR (75 Mz, CDCl 3 ): δ , , , , , , , , 84.84, 83.16, 55.86, 51.67, 51.25, 38.73, 21.59, 19.05; IR (neat): 2920, 2365, 1600, 1480, 1425, 1395, 1345, 1320, 1305, 1185, 1160, 1010, 930, 900, 835, 805, 750, 665, 590, 510, 431 cm -1 ; RMS (ESI positive): calcd. for C BrO 3 Sa [M + a] + = , found m.p.: C (20% EA, 80% C). S6

7 (3-(4-Methoxyphenyl)-prop-2-ynyl)-4-methyl--[(2-methyloxiran- 2-yl)-methyl]-benzene-sulfonamide (12) According to GP3, S6 S6 (1.11 g, 3.00 mmol) was treated with mcpba (960 mg, 3.90 mmol) in C 2 Cl 2 (45.0 ml). The crude product was purified by SiO 2 chromatography (9% EA in C, R f = 0.17 (18% EA in C)) to give 12 (434 g, 1.11 mmol, 38%) as a yellow oil. 1 -MR (400 Mz, C 6 D 6 ): δ 7.90 (dt, J = 8.44 z, 2), (m, 2), 6.88 (d, J = 7.68 z, 2), (m, 2), 4.62 (d, J = z, 1), 4.53 (d, J = z, 1), 3.53 (d, J = z, 1), 3.42 (d, J = z, 1), 3.27 (s, 3), 2.56 (d, J = 5.04 z, 1), 2.27 (d, J = 4.66 z, 1), 1.97 (s, 3), 1.34 (s, 3); 13 C-MR (100 Mz, C 6 D 6 ): δ , , , , , , , , 85.95, 81.40, 55.42, , 51.16, 38.78, 21.10, 18.85; IR (neat): 2925, 2840, 2360, 2340, 1650, 1570, 1510, 1440, 1345, 1305, 1245, 1160, 1100, 1030, 965, 925, 900, 830, 700, 565, 495, 410 cm -1 ; RMS (ESI positive): calcd. for C O 4 Sa [M + a] + = , found (4-Phenyl-but-3-ynyl)-cyclohexanone (S14) According to GP2, S13 S1 (1.80 g, 12.0 mmol) was treated with iodobenzene (2.69 g, 13.2 mmol), CuI (46.0 mg, 0.24 mmol), Pd(PPh 3 ) 2 Cl 2 (168 mg, 0.24 mmol) in Et 3 (70 ml) at 50 C for 16 h. The crude product was purified by bulb to bulb destillation (4*10-1 mbar, 162 C, R f = 0.30 (6% EA in C)) to give S14 (2.24 g, 9.91 mmol, 83%) as a colorless oil. 1 -MR (300 Mz, CDCl 3 ): δ (m, 2), (m, 3), (m, 6), (m, 3), (m, 1), (m, 2), (m, 3); 13 C-MR (75 Mz, CDCl 3 ): δ , , , , , 89.80, 81.05, 49.45, 42.31, 34.08, 28.56, 28.16, 25.23, 17.25; IR (neat): 2930, 2860, 1705, 1600, 1490, 1440, 1340, 1310, 1130, , 975, 915, 825, 755, 690., 540, 490, 415 cm -1 ; RMS (ESI positive): calcd. for C Oa [M + a] + = , found S7

8 (4-Phenyl-but-3-ynyl)-1-oxaspiro-[2.5]-octane (16) O Ph C 2 Br 2, n-buli O Ph TF, -78 C to rt, 16 h S14 16 To a solution of S14 (678 mg, 3.00 mmol) in TF (25.0 ml) C 2 Br 2 (710 mg, 4.00 mmol) was added and cooled down to -78 C. n-buli (1.97 ml, 3.15 mmol) (1.6 M in hexane) was added very slowly (syringe pump). The mixture stirred for 16 h at room temperature. MTBE (50.0 ml) was added and the mixture was washed with aq. sat. 4 Cl (2x50 ml), dried over MgSO 4. After removal of solvent using rotary evaporator, the crude compound was purified by SiO 2 chromatography (3% EA in C, R f = 0.54 (6% EA in C)) to give 16 (640 mg, 2.66 mmol, 89%, d.r. = 99:1) as a pale yellow oil. 1 -MR (300 Mz, C 6 D 6 ): δ (m, 2), (m, 3), 2.45 (dd, J = 4.91 z, J = 0.94 z, 1), (m, 2), 2.23 (d, J = 4.91 z, 1), (m, 1), (m, 10); 13 C-MR (75 Mz, CDCl 3 ): δ , , , , 90.68, 81.49, 60.37, 52.65, 39.79, 32.47, 29.57, 28.34, 25.26, 22.97, 17.28; IR (neat): 3040, 2930, 2855, 1600, 1490, 1440, 1340, 1260, 1155, 1070, 925, 845, 755, 690, 525, 400 cm -1 ; RMS (EI positive): calcd. for C O [M] + = , found Catalytic radical cyclizations terminated by Ir-catalyzed AT [trans-9-methyl-7-(4-toluene-sulfonyl)-7-aza-cis-bicyclo-[4.3.0]-non-1-yl]-methanol (3) O cat. 1, cat.cp 2 TiCl 2, Coll*Cl, Mn, 2 (4bar) rt, 48 h 2 3 According to GP1, 2 (160 mg, 0.5 mmol) was treated with 1 (39 mg, 50 µmmol), Cp 2 TiCl 2 (8.9 mg, 37 µmol), 2,4,6-Me 3 Py*Cl (118 mg, 0.75 mmol), Mn (82.5 mg, 1.50 mmol) in TF (3 ml) at room temperature and 4 bar hydrogen pressure for 48 h. The crude product was purified by SiO 2 chromatography (22% EA in C, R f = 0.15 and R f = 0.11) to give 3 (153 mg, 0.47 mmol, 94%, d.r. = 74:26) as a colorless solid. S8

9 O cat. Cp 2 TiCl 2, Coll*Cl, Mn rt, 48 h 2 3 To a dry schlenk flask under argon atmosphere 2 (160 mg, 0.5 mmol) was added to a solution of Cp 2 TiCl 2 (8.9 mg, 37 µmol), 2,4,6-Me 3 Py*Cl (118 mg, 0.75 mmol), Mn (82.5 mg, 1.50 mmol) in TF (3 ml). The resulting mixture stirred for 48 h at room temperature. The work up follows GP1. The crude product was purified by SiO 2 chromatography to give 3 (68.9 mg, 0.21 mmol, 43%, d.r.: 72:28) and 2 (85.4 mg, 0.27 mmol, 53%). Analyticalal data in agreement with published data. S (4-Ethylidene-3-methyl-1-tosyl-pyrrolidin-3-yl)-methanol (5) O cat. 1, cat.cp 2 TiCl 2, Coll*Cl, Mn, 2 (4bar) rt, 48 h 4 5 According to GP1, 4 (147 mg, 0.5 mmol) was treated with 1 (19.5 mg, 25 µmmol), Cp 2 TiCl 2 (18.4 mg, 75 µmol), 2,4,6-Me 3 Py*Cl (118 mg, 0.75 mmol), Mn (82.5 mg, 1.50 mmol) in TF (3 ml) at room temperature and 4 bar hydrogen pressure for 48 h. The crude product was purified by SiO 2 chromatography (30% EA in C, R f = 0.17) to give 5 (118 mg, 0.40 mmol, 80%, d.r. = 56:44) as a pale yellow oil. O cat. Cp 2 TiCl 2, Coll*Cl, Mn, rt, 48 h 4 5 To a dry schlenk flask under argon atmosphere 4 (147 mg, 0.5 mmol) was added to a solution of Cp 2 TiCl 2 (18.4 mg, 75 µmol), 2,4,6-Me 3 Py*Cl (118 mg, 0.75 mmol), Mn (82.5 mg, 1.50 mmol) in TF (3 ml). The resulting mixture stirred for 48 h at room temperature. The work up follows GP1. The crude product was purified by SiO 2 chromatography(30% EA in C, R f = 0.17) to give 5 (54.7 mg, 0.19 mmol, 37%, d.r.: 60:40) as a pale yellow oil and 4 (65.7 mg, 0.22 mmol, 45%). S9

10 Major diastereomer: 1 -MR (300 Mz, CDCl 3 ): δ 7.61 (d, J = 8.31 z, 2), 7.23 (d, J = 8.12 z, 2), (m, 1), (m, 1), (m, 3), 2.68 (d, J = 9.44 z, 1), 2.33 (s, 3), (b, 1), 1.45 (d, J = 6.80 z, 3), 0.97 (s, 3); 13 C-MR (75 Mz, CDCl 3 ): δ , , , , , 67.74, 56.51, 50.20, 47.52, 21.67, 14.64; Minor diastereomer: 1 -MR (300 Mz, CDCl 3 ): δ 7.57 (d, J = 8.50 z, 2), 7.22 (d, J = 8.12 z, 2), 5.30 (q, J = 7.24 z, 1), (m, 1), (m, 3), 2.69 (d, J = 9.25 z, 1), 2.33 (s, 3), (b, 1), 1.56 (d, J = 7.18 z, 3), 1.13 (s, 3); 13 C-MR (75 Mz, CDCl 3 ): δ , ,131.83, , , 66.53, 58.26, 54.47, 47.65, 21.67, 13.68; IR (neat): 3525, 2925, 2360, 1495, 1335, 1245, 1155, 1090, 815, 745, 725, 660, 585, 545, 405 cm -1 ; RMS (ESI positive): calcd. for C O 3 S [M+] + = , found (3-Methyl-4-methylene-1-tosyl-pyrrolidin-3-yl)-methanol (7) O cat. 1, cat.[ti], Coll*Cl, Mn, 2 (4bar) rt, 68 h 6 7 According to GP1, 6 (279 mg, 1.0 mmol) was treated with 1 (39.0 mg, 50 µmmol), Cp 2 TiCl 2 (36.8 mg, 0.15 mmol), 2,4,6-Me 3 Py*Cl (236 mg, 1.50 mmol), Mn (165 mg, 3.00 mmol) in TF (5 ml) at room temperature and 4 bar hydrogen pressure for 68 h. The crude product was purified by SiO 2 chromatography (30% EA in C, R f = 0.41 (40% EA in C)) to give 7 (203 mg, 0.72 mmol, 72%) as a pale yellow oil. ) 2 TiCl 2 S15 S10

11 According to GP1, 6 (279 mg, 1.0 mmol) was treated with 1 (39.0 mg, 50 µmmol), Kagan`s complex (S15) (78.8 mg, 0.15 mmol), 2,4,6-Me 3 Py*Cl (236 mg, 1.50 mmol), Mn (165 mg, 3.00 mmol) in TF (5 ml) at room temperature and 4 bar hydrogen pressure for 68 h. The crude product was purified by SiO 2 chromatography to give 7 (216 mg, 0.77 mmol, 77%, e.r. = 63:37) as a pale yellow oil. The value of enantiomeric excess was determined by chiral PLC (Column: KAUER Eurocel 01 (5μm - 4.6mm 250mm).Condition: 20 C; n-hexane:2-propanol = 90:10; flow rate 1.0 ml/min.). Retention time = 11.6 min, Retention time = 13.3 min; 1 -MR (300 Mz, CDCl 3 ): δ 7.58 (d, J = 8.31 z, 2), 7.22 (d, J = 8.12 z, 2), 4.88 (t, J = 1.98 z, 2), 4.77 (t, J = 2.46 z, 2), 3.81 (dt, J = z, J = 2.27 z, 1), 3.65 (dt, J = z, J = 2.08 z, 1), 3.33 (d, J = 9.44 z, 2), 3.19 (d, J = z, 1), 2.72 (d, J = 9.44 z, 1), 2.32 (s, 3), 0.98 (s, 3); 13 C-MR (75 Mz,CDCl 3 ): δ , , , , , , 67.50, 56.40, 52.48, 47.86, 21.64, 20.78; IR (neat): 3525, 2925, 2870, 2360, 1660, 1570, 1335, 1290, 1155, 1090, 1040, 1000, 900, 815, 710, 545, 490 cm -1 ; RMS (ESI positive): calcd. for C O 3 S [M+a] + = , found (E)-(4-Benzylidene-3-methyl-1-tosyl-pyrrolidin-3-yl)-methanol (9) According to GP1, 8 (178 mg, 0.5 mmol) was treated with 1 (19.5 mg, 25 µmmol), Cp 2 TiCl 2 (18.4 mg, 75 µmmol), 2,4,6-Me 3 Py*Cl (118 mg, 0.75 mmol), Mn (82.5 mg, 1.50 mmol) in TF (3 ml) at room temperature and 4 bar hydrogen pressure for 68 h. The crude product was purified by SiO 2 chromatography (30% EA in C, R f = 0.25) to give 9 (135 mg, 0.38 mmol, 76%, d.r. = 96:4) as a pale yellow solid. 1 - MR (300 Mz, CDCl 3 ): δ 7.74 (d, J = 8.12 z, 2), 7.36 (d, J = 7.93 z, 2), (m, 3), 7.13 (d, J = 7.18 z, 2), 6.55 (s, 1), 4.05 (dd, J = z, J = 2.08 z, 1), 3.92 (dd, J = z, J = 2.08 z, 1), 3.41 (d, J = 9.44 z, 1), 3.39 (d, J = z, 1), 3.30 (d, J = z, 1), 2.96 (d, J = 9.25 z, 1), 2.46 (s, 3), 1.04 (s, 3); 13 C-MR (75 Mz,CDCl 3 ): δ , , , , , , , , , , 66.25, 58.15, 54.68, 48.50,21.94, 21.74; IR (neat): 3485, 2920, 2875, 2360, 2340, 1475, 1395, 1335, 1305, 1185, 1150, 1020, 1000, 920, 845, 815, 700, 665, 585, 490, 415 cm -1 ; RMS (ESI positive): calcd. for C O 3 S [M+a] + = , found ; m.p.: C (30% EA, 70% C). S11

12 The structure was further confirmed by OE study ( 1 -MR (500 Mz, CDCl 3 )): Proton/Protons irradiated δ OE observed , , 5, , (E)-(4-(4-Bromobenzylidene)-3-methyl-1-tosyl-pyrrolidin-3-yl)-methanol (11) According to GP1, 10 (217 mg, 0.5 mmol) was treated with 1 (19.5 mg, 25 µmmol), Cp 2 TiCl 2 (18.4 mg, 75 µmol), 2,4,6-Me 3 Py*Cl (118 mg, 0.75 mmol), Mn (82.5 mg, 1.50 mmol) in TF (3 ml) at room temperature and 4 bar hydrogen pressure for 68 h. The crude product was purified by SiO 2 chromatography (30% EA in C, R f = 0.30 and R f = 0.09) to give 11 (153 mg, 0.35 mmol, 70%, d.r. = 91:9) as a colorless solid. 1 -MR (300 Mz, CDCl 3 ): δ 7.73 (dt, J = 8.31 z, J = 1.70 z, 2), 7.41 (d, J = 8.31 z, 2), 7.36 (d, J = 7.93 z, 2), 7.01 (d, J = 7.93 z, 2), 6.44 (s, 1), 4.00 (dd, J = z, J = 2.08 z, 1), 3.93 (dd, J = z, J = 2.23 z, 1), 3.41 (d, J = 9.44 z, 1), 3.36 (q, J = z, 2), 2.93 (d, J = 9.44 z, 1), 2.46 (s, 3), 1.01 (s, 3); 13 C-MR (75 Mz,CDCl 3 ): δ , , , , , , , , , , 66.51, 58.13, 54.71, 48.51, 21.75, 21.69; IR (neat): 3555, 2930, 2870, 2360, 2340, 1595, 1480, 1390, 1330, 1310, 1300, 1180, 1155, 1120, 1085, 1070, 1010, 980, 835, 710, 640, 595, 525, 455, 430 cm -1 ; RMS (ESI positive): calcd. for C BrO 3 S [M+a] + = , found ; m.p.: (30% EA, 70% C). S12

13 3.6. (E)-(4-(4-Methoxybenzylidene)-3-methyl-1-tosyl-pyrrolidin-3-yl)-methanol (13) According to GP1, 12 (193 mg, 0.5 mmol) was treated with 1 (19.5 mg, 25 µmmol), Cp 2 TiCl 2 (18.4 mg, 75 µmol), 2,4,6-Me 3 Py*Cl (118 mg, 0.75 mmol), Mn (82.5 mg, 1.50 mmol) in TF (3 ml) at room temperature and 4 bar hydrogen pressure for 48 h. The crude product was purified by SiO 2 chromatography (25% EA in C, R f = 0.06) to give 13 (135 mg, 0.35 mmol, 70%, d.r. = 89:11) as a pale yellow solid. 1 -MR (300 Mz, CDCl 3 ): δ 7.73 (d, J = 8.12 z, 2), 7.35 (d, J = 7.74 z, 2), 7.05 (d, J = 8.67 z, 2), 6.81 (d, J = 8.67 z, 2), 6.47 (s, 1), (m, 1), 3.89 (dd, J = z, J = 1.89 z, 1), 3.79 (s, 3), (m, 3), 2.97 (d, J = 9.06 z, 1), 2.45 (s, 3), 1.06 (s, 3); 13 C-MR (75 Mz,CDCl 3 ): δ , , , , , , , , , , 66.07, 58.20, 55.38, 54.69, 48.40, 21.93, 21.73; IR (neat): 3550, 2930, 2835, 1605, 1510, 1465, 1335, 1240, 1155, 1120, 1090, 1035, 870, 820, 770, 710, 665, 605, 550, 510, 465, 405 cm -1 ; RMS (ESI positive): calcd. for C O 4 S [M+a] + = , found ; m.p.: C (25% EA, 75% C) (9-Ethylidene-cis-bicyclo-[4.3.0]-nonyl)-methanol (15) O cat. 1, cat.cp 2 TiCl 2, Coll*Cl, Mn, 2 (4bar) rt, 68 h According to GP1, 14 (178 mg, 1.0 mmol) was treated with 1 (8.0 mg, 10 µmmol), Cp 2 TiCl 2 (24.5 mg, 0.10 mmol), 2,4,6-Me 3 Py*Cl (236 mg, 1.50 mmol), Mn (165 mg, 3.00 mmol) in TF (5 ml) at room temperature and 4 bar hydrogen pressure for 68 h. The crude product was purified by SiO 2 chromatography (5% EA in C, R f = 0.16) to give 15 (108 mg, 0.60 mmol, 60%, d.r. = 63:37) as a colorless oil. According to GP1, 14 (178 mg, 1.0 mmol) was treated with 1 (39.0 mg, 50 µmmol), Cp 2 TiCl 2 (24.5 mg, 0.10 mmol), 2,4,6-Me 3 Py*Cl (236 mg, 1.50 mmol), Mn (165 mg, 3.00 mmol) in TF (5 ml) at room S13

14 temperature and 4 bar hydrogen pressure for 68 h. The crude product was purified by SiO 2 chromatography to give 15 (127 mg, 0.71 mmol, 71%, d.r. = 63:37) as a colorless oil. According to GP1, 14 (178 mg, 1.0 mmol) was treated with 1 (39.0 mg, 50 µmmol), Cp 2 TiCl 2 (36.8 mg, 0.15 mmol), 2,4,6-Me 3 Py*Cl (236 mg, 1.50 mmol), Mn (165 mg, 3.00 mmol) in TF (5 ml) at room temperature and 4 bar hydrogen pressure for 20 h. The crude product was purified by SiO 2 chromatography to give 15 (158 mg, 0.88 mmol, 88%, d.r. = 63:37) as a colorless oil. Analytical data in agreement with published data. S (9-Benzylidene-cis-bicyclo-[4.3.0]-nonyl)-methanol (17) O Ph cat. 1, cat.cp 2 TiCl 2, Coll*Cl, Mn, 2 (4bar) Ph rt, 20 h According to GP1, 16 (120 mg, 0.5 mmol) was treated with 1 (19.5 mg, 25 µmmol), Cp 2 TiCl 2 (18.4 mg, 75 µmol), 2,4,6-Me 3 Py*Cl (118 mg, 0.75 mmol), Mn (82.5 mg, 1.50 mmol) in TF (3 ml) at room temperature and 4 bar hydrogen pressure for 20 h. The crude product was purified by SiO 2 chromatography (3% EA in C, R f = 0.13 and R f = 0.09 (6% EA in C)) to give 17 (82.0 mg, 0.34 mmol, 68%, d.r. = 84:16) as a pale yellow solid. 1 -MR (300 Mz, CDCl 3 ): δ (m, 5), 6.49 (s, 1), 3.42 (dd, J = z, J = 8.88 z, 2), 3.14 (dd, J = z, J = 1.89 z, 2), (m, 2), (m, 1), (m, 9); 13 C-MR (75 Mz,CDCl 3 ): δ , , , , , , 64.77, 50.97, 40.72, 33.56, 30.41, 26.44, 25.88, 22.55, 22.02; IR (neat): 3315, 2930, 2850, 2360, 2340, 1475, 1445, 1110, 1090, 1070, 1020, 955, 930, 860, 840, 820, 750, 700, 610, 555, 525, 490, 420, 410 cm -1 ; RMS (EI positive): calcd. for C O [M] + = , found ; m.p.: C (3% EA, 97% C). S14

15 3.9. (10-Ethylidene-cis-bicyclo-[5.3.0]-dec-1-yl)-methanol (19) O cat. 1, cat.cp 2 TiCl 2, Coll*Cl, Mn, 2 (4bar) rt, 68 h According to GP1, 18 (192 mg, 1.0 mmol) was treated with 1 (39.0 mg, 50 µmmol), Cp 2 TiCl 2 (36.8 mg, 0.15 mmol), 2,4,6-Me 3 Py*Cl (236 mg, 1.50 mmol), Mn (165 mg, 3.00 mmol) in TF (5 ml) at room temperature and 4 bar hydrogen pressure for 68 h. The crude product was purified by SiO 2 chromatography (2% EA in C) to give 19 (177 mg, 0.91 mmol, 91%, d.r. = 67:33) as a colorless oil. Analytical data in agreement with published data. S1 4. ydrogenation reactions of 15 and 19 with Crabtree s catalyst 4.1. (trans-9-ethyl-cis-bicyclo[4.3.0]non-1-yl)-methanol (S16) cat. S17, 2 (1bar) C 2 Cl 2,-95 Ctort, 16 h 15 S16 To a degassed solution of 15 (90.0 mg, 0.50 mmol) and C 2 Cl 2 (4 ml) under an argon atmosphere Crabtree`s catalyst [Ir(cod)PCy 3 (py)]pf 6 (S17) (12.5 µmol, 10.1 mg) was added. The solution was degassed one more time and was allowed to reach room temperature under a hydrogen atmosphere. The mixture stirred for 16 hours at room temperature before the solvent was removed under reduced pressure. Ether was added and filtered over silica gel. The crude product was purified by SiO 2 chromatography (6% EA in C, R f = 0.38) to give S16 (87 mg, 0.48 mmol, 96%, d.r. = 99:1) as a pale yellow oil. 1 -MR (300 Mz, CDCl 3 ): δ 3.65 (d, J = z, 1), 3.53 (d, J = z, 1), (m, 2), (m, 2), (m, 3), (m, 6), ,12 (m, 4), 0.86 (t, J = 7.27 z, 3); 13 C-MR (75 Mz,CDCl 3 ): δ 65.13, 47.91, 45.52, 38.94, 27.50, 25.39, 24.76, 24.02, 22.55, 21.98, 20.51, 13.38; IR (neat): 3315, 2920, 2860, 1460, 1375, 1245,1120, 1050, 1020, 1000, 670, 905, 845, 775, 605, 525, 510, 445cm -1. The mixture of cis- and trans-isomers was characterized in reference S1. S15

16 4.2. (trans-10-ethyl-cis-bicyclo[5.3.0]dec-1-yl)-methanol (S18) cat. S17, 2 (1bar) C 2 Cl 2,-95 Ctort, 16 h 19 S18 To a degassed solution of 19 (194 mg, 1.00 mmol) and C 2 Cl 2 (8 ml) under an argon atmosphere S17 (25.0 µmol, 20.2 mg) was added. The mixture was treated as described at the preparation of S16. The crude product was purified by SiO 2 chromatography (5% EA in C, R f = 0.12 (9%EA in C)) to give S18 (179 mg, 0.92 mmol, 92%, d.r. = 99:1) as a colorless oil. 1 -MR (400 Mz, CDCl 3 ): δ 3.58 (d, J = z, 1), 3.32 (d, J = z, 1), (m, 6), (m, 12), (m, 1), 0.89 (t, J = 7.37 z, 3); 13 C-MR (100 Mz,CDCl 3 ): δ 69.94, 50.75, 49.39, 47.62, 34.01, 34.00, 32.69, 31.49, 29.74, 29.26, 28.44, 27.07, 24.11, 23.64; IR (neat): 2215, 2915, 2850, 1450, 1375, 1245, 1040, 1020, 990, 980, 945, 880, 835, 765, 650, 575, 460, 405cm -1 ; RMS (EI positive): calcd. for C [M- 2 O] + = , found ; References S1) Gansäuer, A.; Pierobon, M.; Bluhm,. Synthesis 2001, 16, S2) Kataoka, T.; Yoshimatsu, M.; oda, Y.; Sato, T.; Shimizu,.; ori, M. J. Chem. Soc. Perkin Trans , 1, S3) ashmi, A. S. K.; Weyrauch, J. P.; Kurpejovic, E.; Frost, T. M.; Michlich, B.; Frey, W.; Bats, J. W. Chem. Eur. J. 2006, 12, S4) Madhushaw, R. J.; Li, C.-L.; Su.-L.; u, C.-C.; Lush, S.-F.; Liu, R.-S. J. Org. Chem. 2003, 68, S5) Shibata, T.; Kobayashi, Y.; Maekawa, S.; Toshida,.; Takagi, K. Tetrahedron 2005, 61, S6) Fürstner, A.; Davies, P. W.; Grees, T. J. Am. Chem. Soc. 2005, 127, S16