Supporting Information

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1 Supporting Information Asymmetric Diels-Alder Reaction of a,b-unsaturated xazolidin-2-one Derivatives Catalyzed by a Chiral Fe(III)-Bipyridine Diol Complex Mao Li, Virginie Carreras, Angela Jalba, Thierry llevier* Département de chimie, Université Laval, 1045 avenue de la Médecine, Québec, QC G1V 0A6, Canada Fax: ; thierry.ollevier@chm.ulaval.ca Table of Contents General Information S-2 Characterization of Dienophiles S-2 General Procedures for Asymmetric Diels-Alder Reactions S-5 Representative Procedure for Asymmetric Diels-Alder Reaction S-5 Characterization of Cycloadducts S-6 References S-12 MR Spectra and HPLC Chromatograms S-13 S-1

2 General Information All reactions were performed in flame-dried glassware under an atmosphere of argon. The following reaction solvents were distilled from the indicated drying agents: dichloromethane (CaH2), THF (a, benzophenone), CH3C (CaH2), and dichloroethane (CaH2). Fe(Cl 4) 3. 6H 2 was purchased from Alfa Aesar (reagent grade purity). ther chemicals, such as isoprene, butadiene, 2,3-dimethylbuta-1,3-diene, and cyclohexa-1,3-diene, were purchased from Sigma-Aldrich or Alfa Aesar. 1 H and 13 C spectra were recorded on Bruker 300 MHz, Varian Inova 400 MHz, and Agilent Technologies DD2 500 MHz spectrometer in CDCl3. 19 F spectra was recorded on Agilent Technologies DD2 500 MHz spectrometer in CDCl3 without external standard. For 1 H MR, tetramethylsilane (TMS) served as internal standard (δ = 0 ppm) and data are reported as follows: chemical shift (in ppm), multiplicity (s = singlet, d = doublet, t = triplet, q =quartet, m = multiplet, br = broad), coupling constant (in Hz), and integration. For 13 C MR, CDCl3 was used as internal standard (δ = ppm) and spectra were obtained with complete proton decoupling. IR spectra were recorded on a BMEM Arid-Zone TM FT-IR spectrometer and are reported in reciprocal centimeters (cm 1 ). Flash column chromatography was performed on silica gel ( mesh). ptical rotations were measured on a Jasco DIP-360 digital polarimeter with a sodium lamp and are reported as follows: [α]d T (c g/100 ml, solvent). High-resolution mass spectra (HRMS) were recorded on an LC/MS-TF (time of flight) Agilent 6210 mass spectrometer. Melting point (mp) are uncorrected and were recorded on a MEL-TEMP capillary melting point apparatus. Enantiomeric ratios were determined on an Agilent 1100 Series HPLC system (Hexanes/iPrH solvent mixture) using Daicel ChiralCel J H, and ChiralPak AD H columns. Caution: Perchlorate salts can be explosive and should be handled with care. Conversion to lower hydrates by unintentional dehydration may cause explosion. Use due caution in handling, as for all perchlorates. 1 Characterization of Dienophiles 3-Acryloyloxazolidin-2-one (2a). 2 The dienophile was synthesized according to the following procedure. To a solution of oxazolidin-2-one (10 g, 115 mmol) in anhydrous THF (200 ml) at 0 C under argon atmosphere and magnetic stirring, triethylamine (40 ml, 288 mmol) was added. After 0.5 h, acryloyl chloride (19 ml, 230 mmol) was added dropwise and the mixture was stirred at 0 C for another 2 hours and then up to room temperature. The reaction was quenched by H 4Cl aqueous solution (100 ml) after 15 h, and the resulting mixture was diluted with dichloromethane and washed successively with saturated solutions of ahc 3 and acl. Concentrated HCl was added to adjust the ph to acidic condition (ph = 3). The organic phase was dried over anhydrous MgS 4, filtered, and concentrated in vacuo. The pure product (8.6 g, 61 mmol, 53%) was obtained as a white solid by flash chromatography on silica gel. R f = 0.24 (Hexanes/AcEt = 80:20). mp = C (litt. 2 mp = C). 1 H MR (400 MHz, CDCl 3) δ H 7.50 (dd, J = 17.0, 10.5 Hz, 1H), 6.56 (dd, J = 17.0, 0.9 Hz, 1H), 5.91 (dd, J = 17.0, 0.9 Hz, 1H), 4.45 (t, J = 8.0 Hz, 2H), 4.09 (t, J = 8.0 Hz, 2H) ppm. 13 C MR (126 MHz, CDCl 3) δ C 165.0, S-2

3 153.4, 131.8, 127.0, 62.2, 42.6 ppm. IR (acl): 1772, 1687, 1651, 1397, 1232 cm 1. (E)-3-(But-2-enoyl)oxazolidin-2-one (2b). 3 The product was obtained as a colorless solid (3 g, 19.3 mmol, 84%) according to a literature method. 2 R f = 0.24 (Hexanes/AcEt = 80:20). mp = C (litt. 3 mp = 30 C). 1 H MR (400 MHz, CDCl 3) δ H (m, 2H), 4.42 (t, J = 8.0 Hz, 2H), 4.06 (t, J = 8.1 Hz, 2H), 1.96 (dd, J = 5.5, 0.8 Hz, 3H) ppm. 13 C MR (126 MHz, CDCl 3) δ C 164.8, 153.5, 146.0, 121.3, 62.1, 42.3, 18.1 ppm. IR (acl): 2975, 2918, 1778, 1685, 1638, 1389, 1223, 1044, 708 cm 1. 3-Cinnamoyloxazolidin-2-one (2c). 4 The product was obtained as white crystals (2.2 g, 10.1 mmol, 89%) according to a literature method. 5 R f = 0.20 (Hexanes/AcEt = 80:20). mp Ph = C (litt. 6 mp = C). 1 H MR (400 MHz, CDCl 3) δ H (m, 2H), (m, 2H), (m, 3H), 4.46 (td, J = 8.3, 1.5 Hz, 2H), (m, 2H) ppm. 13 C MR (126 MHz, CDCl 3) δ C 165.4, 153.6, 146.3, 134.5, 130.7, 128.9, 128.7, 116.6, 62.1, 42.8 ppm. IR (acl): 1767, 1677, 1619, 1479, 1448, 1355 cm 1. (E)-3-(4,4,4-Trifluorobut-2-enoyl)oxazolidin-2-one (2d). 7 The product was obtained as a yellow solid (1.4 g, 6.4 mmol, 50%) according to a literature method. 5 R f = 0.24 F 3 C (Hexanes/AcEt = 80:20). mp = C (litt. 8 mp = C). 1 H MR (300 MHz, CDCl 3) δ H 7.90 (dq, J = 15.5, 2.0 Hz, 1H), 6.89 (dq, J = 15.5, 6.6 Hz, 1H), 4.49 (t, J = 8.0 Hz, 2H), 4.11 (t, J = 8.0 Hz, 2H) ppm. 13 C MR (75 MHz, CDCl 3,) δ C 162.6, 153.0, (q, J = 35.7 Hz), (q, J = 6.2 Hz), (q, J = Hz), 62.3, 42.5 ppm. IR (acl): 3103, 1772, 1693, 1667, 1378, 1135, 1044, 755 cm 1. 1-Acryloylpyrrolidin-2-one (2e). The product was obtained as a yellow liquid (2.6 g, 18.7 mmol, 80%) following the same method for synthesizing 2a. R f = 0.37 (Hexanes/AcEt = 80:20). 1 H MR (400 MHz, CDCl 3) δ H 7.42 (ddd, J = 17.1, 10.5, 0.8 Hz, 1H), 6.44 (m, 1H), 5.79 (ddd, J = 10.5, 1.9, 0.8 Hz, 1H), (m, 2H), 2.58 (t, J = 8.1 Hz, 2H), 2.01 (dd, J = 13.0, 5.4 Hz, 2H) ppm. 13 C MR (126 MHz, CDCl 3) δ C 175.8, 165.9, 130.6, 129.0, 45.6, 33.6, 17.1 ppm. IR (acl): 3102, 2964, 1738, 1681, 1638, 1409, 1362, 1254 cm 1. HRMS (ESI) [M+H] + calcd for C 7H 10 2 requires , found (Pyrrolidin-1-yl)prop-2-en-1-one (2f). 9 The product was obtained as a yellow liquid (1.3 g, 10.4 mmol, 50%) following the same method for the synthesis of 2a. R f = 0.29 (Hexanes/AcEt = 50:50). 1 H MR (400 MHz, CDCl 3) δ H 6.37 (qd, J = 16.8, 6.2 Hz, 2H), 5.62 (dd, J = 9.9, 2.5 Hz, 1H), 3.50 (td, J = 6.9, 2.5 Hz, 4H), (m, 2H), (m, 2H) ppm. 13 C MR (126 MHz, CDCl 3) δ C 164.3, 128.7, 127.2, 46.5, 45.8, 25.9, 24.2 ppm. IR (acl): 2973, 2876, 1650, 1610, 1441 cm 1. S-3

4 2-Cinnamoylpyridine 1-oxide (2g). 11 The product was obtained as a yellow solid (0.549 g, 2.4 mmol, 61%) according to a literature method. 11 R f = 0.12 (Hexanes/AcEt = 50:50). mp Ph + = C (litt. 12 mp = C). 1 H MR (400 MHz, CDCl 3) δ H 8.25 (d, J = 6.2 Hz, 1H), 7.81 (m, 1H), (m, 4H), (m, 5H) ppm. 13 C MR (126 MHz, CDCl 3) δ C 186.4, 147.2, 144.2, 140.4, 134.5, 130.8, 128.9, 128.8, 127.8, 127.2, 125.8, ppm. IR (acl): 3112, 3025, 1670, 1612, 1427, 1337, 1199, cm 1. (E)-3-Phenyl-1-(pyridin-2-yl)prop-2-en-1-one (2h). 10 The product was obtained as pale green crystals (1.6 g, 7.6 mmol, 90%) according to a literature method. 10 R f = 0.55 (Hexanes/AcEt = 80:20). mp = C (litt. 10 mp = C). 1 H MR Ph (400 MHz, CDCl 3) δ H 8.75 (m, 1H), 8.31 (d, J = 16.1 Hz, 1H), 8.18 (m, 1H), 7.95 (d, J = 16.1 Hz, 1H), 7.88 (td, J = 7.7, 1.7 Hz, 1H), 7.74 (dd, J = 6.3, 3.0 Hz, 2H), 7.49 (ddd, J = 7.5, 4.8, 1.2 Hz, 1H), 7.42 (dd, J = 5.0, 1.7 Hz, 3H) ppm. 13 C MR (126 MHz, CDCl 3) δ C 189.5, 154.2, 148.9, 144.8, 137.0, 135.1, 130.6, 128.9, 128.8, 127.0, 123.0, ppm. IR (acl): 3056, 1671, 1607, 1449, 1336, 753 cm 1. (E)-3-(4-Chlorophenyl)-1-(pyridin-2-yl)prop-2-en-1-one (2i). 10 The product was obtained as a grey solid (1.0 g, 4.1 mmol, 80%) according to a literature method. 10 R f = 0.55 (Hexanes/AcEt = 80:20). mp = C (litt. 10 mp = C). p-clc 6 H 4 1 H MR (400 MHz, CDCl 3) δ H 8.75 (d, J = 5.1 Hz, 1H), 8.29 (d, J = 16.0 Hz, 1H), 8.19 (d, J = 8.0 Hz, 1H), (m, 2H), 7.66 (d, J = 8.4 Hz, 2H), 7.50 (m, 1H), 7.39 (d, J = 8.3 Hz, 2H) ppm. 13 C MR (101 MHz, CDCl 3) δ C 189.3, 154.0, 148.9, 143.2, 137.1, 136.4, 133.6, 130.0, 129.1, 127.0, 123.0, ppm. IR (acl): 2918, 1673, 1608, 1567, 1331, 789 cm 1. (E)-3-(4-Methoxyphenyl)-1-(pyridin-2-yl)prop-2-en-1-one (2j). 10 The product was gained as a green solid (1.8 g, 7.5 mmol, 89%) according to a literature method. 10 R f = p-mec 6 H (Hexanes/AcEt = 80:20). mp = C (litt. 10 mp = C). 1 H MR (500 MHz, CDCl 3) δ H 8.75 (m, 1H), (m, 2H), 7.93 (d, J = 16.0 Hz, 1H), 7.87 (m, 1H), 7.71 (d, J = 8.8 Hz, 2H), 7.49 (m, 1H), 6.95 (d, J = 8.7 Hz, 2H), 3.87 (s, 3H). 13 C MR (126 MHz, CDCl 3) δ C 189.4, 161.7, 154.5, 148.8, 144.7, 137.0, 130.8, 128.0, 126.7, 122.9, 118.5, 114.3, IR (acl): 3650, 1773, 1685, 1597, 1258, 1031 cm 1. S-4

5 General Procedure for Asymmetric Diels-Alder Reactions L* t-bu t-bu H H n Fe(Cl 4 ) 3 6H 2 R 1 n + R 1 R 2 30 C rt, h n = 0, 1, 2 R2 The asymmetric Diels-Alder reaction was carried out in a flame-dried test tube under an argon atmosphere. Fe(Cl 4) 3. 6H 2 and chiral ligand were charged to the test tube, followed by addition of freshly distilled solvent (0.7 ml). This solution was magnetically stirred 1.5 h at room temperature. Then the dienophile (0.5 mmol) and additional freshly distilled solvent (0.3 ml) were added to the solution, successively, at the corresponding temperature, and was stirred for another 0.75 h. Then the cyclopentadiene was added (0.29 ml, 3.5 mmol, 7 equiv) and the solution was stirred at the corresponding temperature for the required time. The reaction was quenched with distilled water (0.3 ml) and the mixture was extracted with ether (5 ml). The combined organic phases were transferred into a vial and the solvent was removed under vacuo. Diastereoisomeric ratio was determined by 1 H MR analysis and followed by purification through silica gel chromatography (CH 2Cl 2/methanol) to afford the desired cycloadduct. Enantiomeric excess of products was determined by chiral HPLC analysis. Representative procedure for asymmetric Diels-Alder reaction The asymmetric Diels-Alder reaction was carried out in a flame-dried test tube under an argon atmosphere. Fe(Cl 4) 3. 6H 2 (9.2 mg, 0.02 mmol, 2 mol %) and chiral L* (8 mg, mmol, 2.4 mol %) were charged to the test tube and followed by addition of freshly distilled MeC (1.4 ml). This solution was stirred 1.5 h at room temperature under magnetic stirring. Afterwards, 3- acryloyloxazolidin-2-one 2a (142 mg, 1 mmol) and the additional freshly distilled MeC (0.6 ml) were added to this mixture solution successively at 30 o C and stirred for another 0.75 h. Then distilled cyclopentadiene 1 was added (0.58 ml, 7 mmol, 7 equiv) and the solution was stirred at 30 C for 1.5 h. The reaction was quenched with distilled water (0.6 ml) and extracted with ether (10 ml). The combined organic phases were transferred into a vial and the solvent was removed under vacuo. Diastereoisomeric ratio was determined by 1 H MR analysis and followed by purification through silica gel chromatography (CH 2Cl 2 = 100%) to afford cycloadduct 3a. Enantiomeric excess of the product was determined by chiral HPLC analysis. S-5

6 Characterization of Cycloadducts (1S,2S,4S)-3-Bicyclo[2.2.1]hept-5-ene-2-carbonyl)oxazolidin-2-one (3a). 13 The product was obtained as a colorless semi-solid (102.6 mg, mmol, 99%) following the above general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: 30 C. Reaction time = 1.5 h. R f = 0.18 (Hexanes/AcEt = 80:20). The diastereomeric ratio was determined from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 92:8). Endo-3a: 1 H MR (500 MHz, CDCl 3) δ H 6.23 (dd, J = 5.3, 2.9 Hz, 1H), 5.86 (dd, J = 5.4, 2.6 Hz, 1H), (m, 2H), (m, 3H), 3.29 (br s, 1H), 2.93 (br s, 1H), 1.94 (m, 1H), (m, 3H) ppm. Exo-3a (significant peaks): δ H 6.16 (s, 2H), (m, 2H), 3.26 (m, 1H), 3.00 (s, 1H), 1.51 (m, 1H), 1.36 (m, 1H) ppm. Endo-3a: 13 C MR (126 MHz, CDCl 3) δ C174.67, , , , 61.96, 50.15, 46.34, 43.14, 42.92, 42.85, ppm. Exo-3a: δ C , , , , 61.90, 46.76, 46.14, 42.95, 41.85, ppm. IR (acl): 2975, 1775, 1696, 1386, 1225, 1040, 1005, 761, 705 cm [α] D = (c = 0.54, CH 2Cl 2) (litt [α] D = (c = 1.02, CHCl 3), 98% ee). 98% ee for endo isomer determined by HPLC (Daicel Chiralpak AD-H, Hexanes/2-propanol = 95:5, flow rate = 1.0 ml/min, λ = 220 nm) minor exo t r = 18.7 min, minor endo t r = 20.0 min, major exo t r = 24.7 min, major endo t r = 26.1 min. (1S,2S,3R,4R)-3-(3-Methylbicyclo[2.2.1]hept-5-ene-2-carbonyl)oxazolidin-2-one (3b). 13 The product was obtained as a colorless solid (105.0 mg, mmol, 95%) following the above general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: 20 C. Reaction time = 24 h. R f = 0.23 (Hexanes/AcEt = 80:20). mp = C (litt. 13 mp = C). The diastereomeric ratio was determined from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 88:12). Endo-3b: 1 H MR (400 MHz, CDCl 3) δ H 6.36 (dd, J = 5.6, 3.1 Hz, 1H), 5.76 (dd, J = 5.7, 2.8 Hz, 1H), 4.39 (td, J = 8.0, 3.1 Hz, 2H), (m, 2H), 3.51 (dd, J = 4.3, 3.5 Hz, 1H), 3.26 (br s, 1H), 2.51 (br s, 1H), 2.07 (m, 1H), 1.69 (d, J = 8.7 Hz, 1H), 1.44 (dq, J = 8.6, 1.6 Hz, 1H), 1.11 (d, J = 7.1 Hz, 3H) ppm. Exo-3b (significant peaks): δ H 6.30 (dd, J = 5.6, 3.1 Hz, 1H), 6.14 (dd, J = 5.6, 2.9 Hz, 1H), 4.03 (t, J = 4.3 Hz, 2H), 2.87 (s, 1H), 2.85 (dd, J = 4.8, 1.2 Hz, 1H), 2.72 (s, 1H), 2.66 (m, 1H), 1.64 (d, J = 8.5 Hz, 1H), 1.36 (dd, J = 8.5, 1.5 Hz, 1H), 0.85 (d, J = 6.9 Hz, 3H) ppm. Endo-3b: 13 C MR (126 MHz, CDCl 3) δ C , , , , 61.89, 51.27, 49.50, 47.46, 47.13, 43.01, 36.43, ppm. Exo-3b: δ C , , , , 61.82, 50.64, 49.52, 47.50, 46.66, 43.07, 37.35, ppm. IR (acl): 2963, 1776, 1696, 1386, 1229, 1100, 770, 735, 705 cm [α] D = (c = 1.06, CH 2Cl 2) (litt [α] D = (c = 1.00, CCl 4), 93% ee). 98% ee for endo isomer determined by HPLC (Daicel Chiralpak AD-H, Hexanes/2-propanol = 99:1, flow rate = 0.5 ml/min, λ = 220 nm) minor exo t r = 50.7 min, minor endo t r = 55.0 min, major exo t r = 60.2 min, major endo t r = 71.2 min. S-6

7 (1S,2R,3R,4R)-3-(3-Phenylbicyclo[2.2.1]hept-5-ene-2-carbonyl)oxazolidin-2-one (3c). 13 The product was obtained as a colorless semi-solid (99.1 mg, mmol, 70%) following the Ph above general procedure, after purification by silica gel chromatography (CH 2Cl 2 = 100%). Reaction temperature: 0 C. Reaction time = 72 h. R f = 0.21 (Hexanes/AcEt = 80:20). The diastereomeric ratio was determined from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 83:17). Endo-3c: 1 H MR (500 MHz, CDCl 3) δ H (m, 5H), 6.54 (dd, J = 5.5, 3.2 Hz, 1H), 5.93 (dd, J = 5.6, 2.7 Hz, 1H), (m, 2H), 4.21 (dd, J = 4.9, 3.6 Hz, 1H), (m, 2H), 3.48 (br s, 1H), 3.37 (d, J = 4.8 Hz, 1H), 3.02 (br s, 1H), 1.97 (d, J = 8.7 Hz, 1H), 1.60 (d, J = 8.7 Hz, 1H) ppm. Exo-3c (significant peaks): δ H (m, 5H), 6.49 (dd, J = 5.5, 3.2 Hz, 1H), 6.05 (dd, J = 5.5, 2.8 Hz, 1H), (m, 2H), (m, 2H), 3.73 (d, J = 5.3 Hz, 1H), 3.14 (s, 1H), 3.11 (s, 1H), 1.85 (d, J = 8.5 Hz, 1H), 1.50 (d, J = 8.5 Hz, 1H) ppm. Endo-3c: 13 C MR (126 MHz, CDCl 3) δ C , , , , , , , , 61.96, 50.31, 49.72, 48.15, 47.48, 46.89, ppm. Exo-3c: δ C , , , , , , , , 61.92, 50.16, 50.03, 49.13, 47.07, 46.79, ppm. IR (acl): 2922, 1775, 1694, 1495, 1477, 1455, 1387, 1224, 1114, 1041, 757, 701 cm [α] D = 62.8 (c = 0.25, CH 2Cl 2) (litt [α] D = (c = 0.37, CCl 4), 51% ee). 80% ee for endo isomer determined by HPLC (Daicel Chiralpak AD-H, Hexanes/2-propanol = 85:15, flow rate = 0.8 ml/min, λ = 220 nm) minor exo t r = 10.1 min, minor endo t r = 11.0 min, major exo t r = 14.4 min, major endo t r = 19.9 min. (1S,2R,3R,4R)-3-(3-Trifluoromethyl)bicyclo[2.2.1]hept-5-ene-2-carbonyl) oxazolidin-2-one (3d). The product was obtained as a white solid (126.5 mg, mmol, 92%) following CF 3 the above general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: 10 C. Reaction time = 8 h. mp = C. R f = 0.21 (Hexanes/AcEt = 80:20). The diastereomeric ratio was determined from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 74:26). 1 H MR (500 MHz, CDCl 3) δ H (m, 1H for endo ((6.38, dd, J = 5.0, 3.6 Hz)), 1H for exo), 6.14 (m, 1H, endo), 5.90 (dd, J = 5.6, 2.8 Hz, 1H, exo), (m, 2H for endo and 2H for exo), (m, 2H for endo and 2H for exo), 3.92 (ddd, J = 11.0, 8.4, 7.3 Hz, 1H, exo), 3.53 (m, 1H, endo), (m, 1H for endo ((3.44, d, J = 5.6 Hz)), and 1H for exo), 3.15 (br s, 1H, endo), 3.10 (d, J = 1.2 Hz, 1H, exo), 3.04 (br s, 1H, endo), 2.76 (qdd, J = 10.3, 5.5, 1.3 Hz, 1H, exo), 1.82 (dd, J = 9.0, 1H, exo), 1.58 (d, J = 8.9 Hz, 1H, endo), 1.51 (d, J = 9.0 Hz, 1H, exo), 1.43 (d, J = 8.9 Hz, 1H, endo) ppm. Endo-3d: 13 C MR (126 MHz, CDCl 3) δ C , , , , (q, J = Hz), 62.11, 49.30, (d, J = 1.0 Hz), (d, J = 1.3 Hz), (q, J = 26.9 Hz), (q, J = 1.7 Hz), ppm. Exo-3d: δ C , , , , (q, J = Hz), 62.13, 46.53, (d, J = 1.3 Hz), (d, J = 1.3 Hz), (q, J = 27.0 Hz), (d, J = 1.7 Hz), ppm. 19 F MR (470 MHz, CDCl 3) δ F (d, J = 9.7 Hz, 3F, endo), (d, J = 10.2 Hz, 3F, exo) ppm. IR (acl): 2990, 1779, 1696, 1362, 1284, 1125, 676 cm [α] D = 28.6 (c = 0.37, CH 2Cl 2). 14% ee for endo isomer determined by HPLC (Daicel Chiralcel J-H, Hexanes/2-propanol = 75:25, flow rate = 0.5 ml/min, λ = 220 nm) minor exo t r = 19.3 min, minor endo t r = 19.9 min, major exo t r = 23.0 min, major endo t r = 25.4 min. HRMS (ESI) [M+a] + calcd for C 12H 12F 3a 3 requires , found S-7

8 (1S,2S,4S)-Bicyclo[2.2.1]hept-5-ene-2-carbonyl)pyrrolidin-2-one (3e). 14 The product was obtained as a colorless oil (97.5 mg, mmol, 95%) following the above general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: -10 C. Reaction time = 8 h. R f = 0.29 (Hexanes/AcEt = 80:20). The diastereomeric ratio was determined from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 90:10). Endo-3e: 1 H MR (400 MHz, CDCl 3) δ H 6.19 (dd, J = 5.5, 3.0 Hz, 1H), 5.81 (dd, J = 5.5, 2.8 Hz, 1H), 3.95 (m, 1H), (m, 2H), 3.22 (br s, 1H), 2.88 (br s, 1H), 2.58 (t, J = 8.1 Hz, 2H, endo), (m, 2H), 1.88 (m, 1H), (m, 3H) ppm. Exo-3e (significant peaks): δ H 6.13 (dd, J = 6.5, 3.2 Hz, 1H), (m, 2H), 2.93 (s, 1H), (m, 3H) ppm. Endo-3e: 13 C MR (101 MHz, CDCl 3) δ C , , , , 50.05, 46.06, 45.93, 44.57, 42.83, 33.99, 29.31, ppm. Exo-3e: δ C , , , , 50.05, 46.62, 45.93, 44.42, 41.88, 33.96, 29.65, ppm. IR (acl): 2970, 1723, 1689, 1460, 1387, 1225, 1044, 838, 695 cm [α] D = (c = 2.5, CH 2Cl 2) (litt [α] D = (c = 2.2, CHCl 3), 97% ee). 96% ee for endo isomer determined by HPLC (Daicel Chiralpak AD-H, Hexanes/2-propanol = 96:4, flow rate = 0.8 ml/min, λ = 220 nm) minor exo t r = 12.0 min, major exo t r = 12.5 min, minor endo t r = 13.6 min, major endo t r = 15.1 min. (1S,2S,4S)-Bicyclo[2.2.1]hept-5-en-2-yl(pyrrolidin-1-yl)methanone (3f). The product was obtained as a brown oil (86.0 mg, mmol, 90%) following the above general procedure, after purification by silica gel chromatography (CH 2Cl 2/Methanol = 99:1). Reaction temperature: 10 C. Reaction time = 36 h. R f = 0.10 (Hexanes/AcEt = 80:20). The diastereomeric ratio from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 78:22). Endo-3f: 1 H MR (500 MHz, CDCl 3) δ H 6.16 (dd, J = 5.3, 3.0 Hz, 1H), 6.01 (dd, J = 5.3, 2.8 Hz, 1H), (m, 2H), (m, 2H), 3.11 (br s, 1H), 2.94 (m, 1H), 2.86 (br s, 1H), (m, 3H), (m, 2H), 1.40 (dd, J = 9.3, 4.7 Hz, 2H), 1.25 (d, J = 7.9 Hz, 1H) ppm. Exo-3f (significant peaks): δ H 6.12 (dd, J = 5.4, 2.8 Hz, 1H), 6.09 (dd, J = 5.6, 2.6 Hz, 1H), (m, 4H), 2.91 (s, 1H), 2.89 (s, 1H), 2.21 (dd, J = 9.2, 4.3 Hz, 1H), (m, 3H), 1.71 (d, J = 8.3 Hz, 1H), 1.33 (d, J = 8.8 Hz, 2H) ppm. Endo-3f: 13 C MR (126 MHz, CDCl 3) δ C , , , 49.62, 46.22, 45.91, 45.05, 43.38, 42.60, 30.36, 26.24, ppm. Exo-3f: δ C , , , 46.54, 46.41, 45.96, 44.91, 43.56, 42.53, 41.58, 26.16, ppm. IR (acl): 2969, 1717, 1633, 1431, 1339, 839, 703 cm 1. HPLC (Daicel Chiralpak AD-H, Hexanes/2- propanol = 99:1, flow rate = 0.6 ml/min, λ = 220 nm) exo t r = 33.0 min, exo t r = 33.7 min, endo t r = 46.6 min, endo t r = 48.7 min. HRMS (ESI) [M+a] + calcd for C 12H 17 requires , found ((1S,2R,3R,4R)-3-Phenylbicyclo[2.2.1]hept-5-ene-2-carbonyl)pyridine 1-oxide (3g). 15 The product was obtained as a colorless oil (129.6 mg, mmol, 89%) following the above Ph general procedure, after purification by silica gel chromatography (CH 2Cl 2/Methanol = 99:1). Reaction temperature: 0 C. Reaction time = 15 h. R f = (Hexanes/AcEt = 50:50). The diastereomeric ratio was determined from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 85:15). Endo- S-8

9 3g 1 H MR (500 MHz, CDCl 3) δ H 8.16 (m, 1H), 7.42 (m, 1H), (m, 6H), 7.18 (m, 1H), 6.46 (dd, J = 5.6, 3.2 Hz, 1H), 5.87 (dd, J = 5.6, 2.7 Hz, 1H), 4.50 (dd, J = 5.1, 3.4 Hz, 1H), 3.38 (s, 1H), 3.35 (d, J = 4.0 Hz, 1H), 3.09 (s, 1H), 1.88 (d, J = 8.6 Hz, 1H), 1.56 (ddd, J = 8.6, 3.5, 1.7 Hz, 1H) ppm. Exo-3g (significant peaks): δ H 6.41 (dd, J = 5.6, 3.1 Hz, 1H), 6.06 (dd, J = 5.6, 2.7 Hz, 1H), 3.91 (ddd, J = 6.6, 5.4, 2.1 Hz, 1H), 3.23 (d, J = 1.4 Hz, 1H), 3.21 (s, 1H), 1.51 (dd, J = 8.6, 1.4 Hz, 1H) ppm. Endo-3g 13 C MR (126 MHz, CDCl 3) δ C , , , , , , , , , , , , 58.21, 49.08, 47.59, 46.36, ppm. Exo-3g: δ C , , , , , , , , , , , , 56.69, 48.84, 48.42, 47.88, ppm. IR (acl): 2974, 1694, 1600, 1548, 1500, 1427, 1293, 1021, 852, 700, 658 cm 1. HPLC (Daicel Chiralpak AD-H, Hexanes/2-propanol = 95:5, flow rate = 1 ml/min, λ = 220 nm) exo t r = 22.6 min, exo t r = 26.5 min, endo t r = 29.6 min, endo t r = 32.3 min. ((1S,2R,3R,4R)-3-Phenylbicyclo[2.2.1]hept-5-en-2-yl)(pyridin-2-yl)methanone (3h). 16 The product was obtained as a white solid (123.8 mg, mmol, 90%) following the above Ph general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: rt. Reaction time = 3 h. R f = 0.74 (Hexanes/AcEt = 80:20). mp = C. The diastereomeric ratio was determined from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 89:11). Endo-3h: 1 H MR (500 MHz, CDCl 3) δ H 8.69 (dd, J = 4.7, 0.6 Hz, 1H), 8.03 (d, J = 7.8 Hz, 1H), 7.82 (td, J = 7.7, 1.7 Hz, 1H), 7.45 (ddd, J = 7.5, 4.8, 1.1 Hz, 1H), (m, 4H), 7.17 (m, 1H), 6.52 (dd, J = 5.5, 3.2 Hz, 1H), 5.86 (dd, J = 5.6, 2.7 Hz, 1H), 4.57 (dd, J = 5.1, 3.5 Hz, 1H), 3.58 (br s, 1H), 3.49 (d, J = 4.5 Hz, 1H), 3.12 (d, J = 1.2 Hz, 1H), 2.10 (d, J = 8.4 Hz, 1H), 1.64 (dd, J = 8.4, 1.6 Hz, 1H) ppm. Exo-3h (significant peaks): δ H 8.67 (dd, J = 4.7, 0.7 Hz, 1H), 8.09 (d, J = 7.8 Hz, 1H), (m, 4H), 6.54 (m, 1H), 6.13 (dd, J = 5.5, 2.8 Hz, 1H), 4.24 (dd, J = 5.3, 0.9 Hz, 1H), 4.06 (dd, J = 5.2, 3.5 Hz, 1H), 3.23 (s, 1H), 3.13 (s, 1H), 1.90 (d, J = 8.5 Hz, 1H), 1.50 (dd, J = 8.5, 1.4 Hz, 1H) ppm. Endo-3h: 13 C MR (126 MHz, CDCl 3) δ C , , , , , , , , , , , , 54.28, 49.37, 48.78, 48.26, ppm. Exo-3h: δ C , , , , , , , , , , , , 52.10, 49.35, 48.99, 47.00, ppm. IR (acl): 2974, 1690, 1600, 1568, 1497, 1332, 1272, 1019, 995, 740 cm [α] D = (c = 0.81, CH 2Cl 2) (litt [α] D = (c = 0.81, CHCl 3), 90% ee for the other enantiomer of 3h). 84% ee for endo isomer determined by HPLC (Daicel Chiralpak AD-H, Hexanes/2-propanol = 98:2, flow rate = 0.5 ml/min, λ = 220 nm) minor exo t r = 18.3 min, major exo t r = 18.7 min, minor endo t r = 21.6 min, major endo t r = 28.7 min. ((1S,2R,3R,4R)-3-(4-Chlorophenyl)bicyclo[2.2.1]hept-5-en-2-yl)(pyridin-2-yl)methanone (3i). 16 The product was obtained as a colorless oil (148.4 mg, mmol, 96%) following p-clc 6 H 4 the above general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: rt. Reaction time = 15 h. R f = 0.59 (Hexanes/AcEt = 80:20). The diastereomeric ratio was determined from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 88:12). Endo-3i: 1 H MR (500 MHz, CDCl 3) δ H 8.67 (m, 1H), 8.01 (dt, J = 7.9, 0.9 Hz, 1H), 7.82 (m, 1H), S-9

10 7.45 (m, 1H), (m, 4H), 6.48 (dd, J = 5.6, 3.2 Hz, 1H), 5.83 (dd, J = 5.6, 2.8 Hz, 1H), 4.47 (dd, J = 5.2, 3.4 Hz, 1H), 3.55 (s, 1H), 3.42 (dd, J = 5.2, 1.7 Hz, 1H), 3.05 (d, J = 1.4 Hz, 1H), 2.01 (d, J = 8.5 Hz, 1H), 1.62 (dd, J = 8.5, 1.7 Hz, 1H) ppm. Exo-3i: (significant peaks): δ H 8.64 (m, 1H), 8.07 (dt, J = 7.8, 0.9 Hz, 1H), 7.42 (m, 1H), (m, 4H), 6.52 (dd, J = 5.6, 3.1 Hz, 1H), 6.06 (dd, J = 5.6, 2.8 Hz, 1H), 4.15 (dd, J = 5.3, 1.2 Hz, 1H), 3.96 (dd, J = 5.2, 3.5 Hz, 1H), 3.16 (s, 1H), 3.11 (d, J = 1.4 Hz, 1H), 1.84 (d, J = 4.1 Hz, 1H), 1.48 (dd, J = 8.6, 1.6 Hz, 1H) ppm. Endo-3i: 13 C MR (126 MHz, CDCl 3) δ C , , , , , , , , , , , , 54.44, 49.23, 48.73, 48.17, ppm. Exo-3i: δ C , , , , , , , , , , , , 52.12, 49.18, 49.01, 47.04, ppm. IR (acl): 2972, 1689, 1582, 1569, 1548, 1491, 1014, 670 cm 1. [α] D 22 = (c = 1.00, CH 2Cl 2). 70% ee for endo isomer determined by HPLC (Daicel Chiralcel D-H, hexanes/2-propanol = 99:1, flow rate = 0.5 ml/min, λ = 254 nm) major exo t r = 13.9 min, minor exo t r = 14.8 min, major endo t r = 16.6 min, minor endo t r = 22.2 min. ((1S,2R,3R,4R)-3-(4-Methoxyphenyl)bicyclo[2.2.1]hept-5-en-2-yl)(pyridin-2-yl)methanone (3j). 16 The product was obtained as a colorless oil (140.4 mg, mmol, 92%) p-mec 6 H 4 following the above general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: 0 o C. Reaction time = 48 h. R f = 0.51 (Hexanes/AcEt = 80:20). The diastereomeric ratio was determined from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 93:7). Endo-3j: 1 H MR (500 MHz, CDCl 3) δ H 8.68 (m, 1H), 8.01 (d, J = 7.9 Hz, 1H), 7.81 (td, J = 7.7, 1.7 Hz, 1H), 7.45 (m, 1H), (m, 2H), 6.84 (dd, J = 8.5, 1.6 Hz, 2H), 6.50 (m, 1H), 5.83 (m, 1H), 4.51 (m, 1H), 3.78 (d, J = 1.8 Hz, 3H), 3.54 (br s, 1H), 3.40 (d, J = 5.0 Hz, 1H), 3.04 (br s, 1H), 2.07 (d, J = 8.4 Hz, 1H), 1.61 (d, J = 8.4 Hz, 1H) ppm. Exo-3j: (significant peaks): δ H 8.66 (m, 1H), 8.07 (d, J = 7.9 Hz, 1H), 7.14 (d, J = 7.3 Hz, 1H), 6.78 (dd, J = 8.5, 1.6 Hz, 2H), 6.52 (m, 1H), 6.11 (m, 1H), 4.16 (d, J = 5.3 Hz, 1H), 3.96 (m, 1H), 3.76 (d, J = 1.8 Hz, 3H), 3.16 (s, 1H), 3.10 (s, 1H), 1.86 (d, J = 8.5 Hz, 1H), 1.47 (d, J = 8.5 Hz, 1H) ppm. Endo-3j: 13 C MR (126 MHz, CDCl 3) δ C , , , , , , , , , , , , 55.25, 54.30, 49.68, 48.72, 48.19, ppm. Exo-3j: δ C , , , , , , , , , , , , 55.19, 52.31, 49.30, 49.07, 47.00, ppm. IR (acl): 2970, 1689, 1610, 1582, 1569, 1512, 1249, 1036, 678, 603 cm [α] D = 23.1 (c = 1.00, CH 2Cl 2). 12% ee for endo isomer determined by HPLC (Daicel Chiralpak AD-H, Hexanes/2-propanol = 98:2, flow rate = 1 ml/min, λ = 220 nm) minor exo t r = 15.0 min, major exo t r = 15.6 min, minor endo t r = 18.4 min, major endo t r = 25.6 min. 3-((1S,2S,4S)-Bicyclo[2.2.2]oct-5-ene-2-carbonyl)oxazolidin-2-one (3k). 17 The product was obtained as a colorless solid (77.4 mg, 0.35 mmol, 70%) following the above general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: 10 C. Reaction time = 3 d. R f = 0.18 (Hexanes/AcEt = 80:20). mp = C. The diastereomeric ratio was determined from 1 H MR analysis performed on the crude reaction mixture (endo/exo = 94:6). Endo-3k: 1 H MR S-10

11 (500 MHz, CDCl 3) δ H 6.34 (m, 1H), 6.16 (t, J = 7.3 Hz, 1H), (m, 2H), 3.98 (t, J = 8.0 Hz, 2H), 3.76 (m, 1H), 2.78 (m, 1H), 2.63 (m, 1H), 1.86 (m, 1H), 1.70 (m, 1H), 1.63 (m, 1H), 1.53 (m, 1H), (m, 2H) ppm. Exo-3k (significant peaks): δ H 4.05 (m, 1H), 3.58 (m, 1H), 2.84 (m, 1H), 2.02 (m, 1H), (m, 2H) ppm. Endo-3k: 13 C MR (75 MHz, CDCl 3) δ C , , , , 61.91, 42.94, 42.00, 32.76, 30.18, 29.47, 25.68, ppm. Exo-3k (significant peaks): δ C , , 61.82, 43.05, 41.77, 32.34, 29.35, 27.89, 25.00, ppm. IR (acl): 2941, 1777, 1699, 1386, 1220, 1041, 761, 695 cm 1. [α] D 22 = 49.3 (c = 0.67, CH 2Cl 2) (litt. 17 [α] D 25 = 51.6 (c = 3.56, CH 2Cl 2, 93% ee). 92% ee for endo isomer determined by HPLC (Daicel Chiralpak AD-H, Hexanes/2-propanol = 85:15, flow rate = 0.8 ml/min, λ = 210 nm) minor exo t r = 28.9 min, major exo t r = 33.5 min, major endo t r = 35.3 min, minor endo t r = 46.5 min. (S)-3-(Cyclohex-3-enecarbonyl)oxazolidin-2-one (3l). 18 The product was obtained as a colorless oil (71.2 mg, mmol, 73%) following the above general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: 0 C. Reaction time = 2.5 d. R f = 0.18 (Hexanes/AcEt = 80:20). 1 H MR (500 MHz, CDCl 3) δ H (m, 2H), (m, 2H), (m, 2H), 3.69 (m, 1H), (m, 4H), 1.93 (m, 1H), 1.63 (m, 1H) ppm. 13 C MR (126 MHz, CDCl 3) δ C 176.4, 153.2, 126.6, 125.0, 62.0, 42.8, 38.1, 27.1, 25.5, 24.6 ppm. IR (acl): 2921, 1775, 1696, 1388, 1223, 1042, 761, 649 cm [α] D = 41.3 (c = 0.76, CH 2Cl 2) (litt [α] D = 20.2 (c = 1.75, CH 2Cl 2, 89% ee of R- 3l). 88% ee determined by HPLC (Daicel Chiralpak AD-H, Hexanes/2-propanol = 90:10, flow rate = 0.5 ml/min, λ = 210 nm) major t r = 26.6 min, minor t r = 28.5 min. (S)-3-(3-Methylcyclohex-3-enecarbonyl)oxazolidin-2-one (3m). 17 The product was obtained as a colorless semi-solid (83.6 mg, 0.40 mmol, 80%) following the above general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: 0 C. Reaction time = 2.5 d. R f = 0.18 (Hexanes/AcEt = 80:20). 1 H MR (500 MHz, CDCl 3) δ H 5.39 (s, 1H), 4.41 (t, J = 8.1 Hz, 2H), 4.03 (t, J = 8.1 Hz, 2H), 3.65 (m, 1H), (m, 3H), (m, 2H), 1.71 (m, 1H), 1.66 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3) δ C 176.6, 153.2, 133.7, 119.0, 61.9, 42.8, 38.1, 29.5, 27.4, 25.9, 23.4 ppm. IR (acl): 2917, 1778, 1697, 1388, 1258, 1040, 761 cm [α] D = 28.6 (c = 0.92, CH 2Cl 2) (litt [α] D = 24.2 (c = 1.40, CH 2Cl 2, 60% ee). 50% ee determined by HPLC (Daicel Chiralcel J-H, hexanes/2-propanol = 80:20, flow rate = 1.0 ml/min, λ = 200 nm) t r = 13.7 min, t r = 14.8 min, t r = 15.4 min, t r = 16.1 min. (S)-3-(3,4-Dimethylcyclohex-3-enecarbonyl)oxazolidin-2-one (3n). 17 The product was obtained as a colorless oil (66.9 mg, 0.30 mmol, 60%) following the above general procedure, after purification by silica gel chromatography (CH 2Cl 2). Reaction temperature: 0 C. Reaction time = 2.5 d. R f = 0.18 (Hexanes/AcEt = 80:20). 1 H MR (500 MHz, CDCl 3) δ H 4.41 (t, J = 8.1 Hz, 2H), 4.03 (t, J = 8.3 Hz, 2H), 3.70 (m, 1H), (m, 6H), 1.62 (s, 6H) ppm. 13 C MR (126 MHz, CDCl 3) δ C 176.7, 153.2, 125.3, 123.7, 61.9, 42.8, 39.0, 33.4, 31.1, 26.2, 19.0, 18.8 ppm. IR (acl): 2925, 1777, 1698, 1391, 1224, 1040, 751 cm -1. S-11

12 [α] D 22 = 15.0 (c = 1.00, CH 2Cl 2) (litt. 17 [α] D 25 = 35.7 (c = 1.96, CH 2Cl 2, 60% ee). 60% ee determined by HPLC (Daicel Chiralpak AD-H, Hexanes/2-propanol = 96:4, flow rate = 0.8 ml/min, λ = 220 nm) major t r = 18.0 min, minor t r = 21.7 min. References (1) M. W. Zettler, Iron(II) Perchlorate, e-ers: Electronic Encyclopedia of Reagent for rganic Synthesis, Wiley-VCH, (2) Buzas, A. K.; Istrate, M. F.; Gagosz, F. Tetrahedron 2009, 65, (3) akamura, T.; shida, M.; omura, T.; akazaki, A.; Kobayashi, S. rg. Lett. 2007, 9, (4) Davies, G. S.; Edwards, J. A.; Walters, A. l. Rec. Trav. Chim. 1995, 114, (5) Andrade, K. Z.; Rocha,. R.; Vercillo,. E.; Silva, W. A.; Matos R. A. F. Synlett 2003, (6) Soloshonok, V. A.; Cai, C.; Hruby, V. J. J. rg. Chem. 2000, 65, (7) Huang, Y; Tokunaga, E.; Suzuki, S.; akamura, S.; Shiro, M.; Shibata,. rg. Lett. 2010, 12, (8) Tamura, K.; Yamazaki, T.; Kitazume, T.; Kubota, T. J. Fluorine Chem. 2005, 126, (9) Shakhmaev, R..; Ishbaeva, A. U.; Sunagatullina, A. S.; Zorin, V. V. Russ. J. Gen. Chem. 2011, 81, (10) tto, S.; Bertoncin, F.; Engberts, J. B. F.. J. Am. Chem. Soc. 1996, 118, (11) Mukherjee, S.; Mondal, S.; Patra, A.; Gonnadeb, R. G.; Biju, A. T. Chem. Commun. 2015, 51, (12) Barroso, S.; Blay, G.; Pedro, J. R. rg. Lett. 2007, 9, (13) Kanemasa, S.; deraotoshi, Y.; Sakaguchi, S.; Yamamoto, H.; Tanaka, J.; Wada, E.; Curran, D. P. J. Am. Chem. Soc. 1998, 120, (14) Sibi, M. P.; Chen, J.; Stanley, L. Synlett 2007, (15) Barroso, S.; Blay, G.; Pedro, J. R. rg. Lett. 2007, 9, (16) Li, Y.; Wang, C.; Hao, J.; Cheng, M.; Jia, G.; Li, C. Chem. Commun. 2015, 51, (17) Evans, A. D.; Barnes, M. D.; Johnson, S. J.; Lectka, T.; Matt, V. P.; Miller J. S.; Murry, A. J.; orcross, D. R.; Shaughnessy, A. E.; Campos, R. K. J. Am. Chem. Soc. 1999, 121, (18) arasaka, K.; Tanaka, H.; Kanai, F. Bull. Chem. Soc. Jpn. 1991, 64, S-12

13 MR Spectra and HPLC Chromatograms 1 H MR spectrum of compound 3a 13 C MR spectrum of compound 3a S-13

14 Chiral HPLC chromatogram of compound 3a (racemic) Chiral HPLC chromatogram of compound 3a S-14

15 1 H MR spectrum of compound 3b 13 C MR spectrum of compound 3b S-15

16 Chiral HPLC chromatogram of compound 3b (racemic) Chiral HPLC chromatogram of compound 3b S-16

17 Ph 1 H MR spectrum of compound 3c Ph 13 C MR spectrum of compound 3c S-17

18 Ph Chiral HPLC chromatogram of compound 3c (racemic) Ph Chiral HPLC chromatogram of compound 3c S-18

19 CF 3 1 H MR spectrum of compound 3d CF 3 13 C MR spectrum of compound 3d S-19

20 CF 3 19 F MR spectrum of compound 3d S-20

21 CF 3 Chiral HPLC chromatogram of compound 3d (racemic) CF 3 Chiral HPLC chromatogram of compound 3d S-21

22 1 H MR spectrum of compound 3e 13 C MR spectrum of compound 3e S-22

23 Chiral HPLC chromatogram of compound 3e (racemic) Chiral HPLC chromatogram of compound 3e S-23

24 1 H MR spectrum of compound 3f 13 C MR spectrum of compound 3f S-24

25 Chiral HPLC chromatogram of compound 3f (racemic) Chiral HPLC chromatogram of compound 3f S-25

26 Ph + 1 H MR spectrum of compound 3g Ph + 13 C MR spectrum of compound 3g S-26

27 Ph + Chiral HPLC chromatogram of compound 3g (racemic) Ph + Chiral HPLC chromatogram of compound 3g S-27

28 Ph 1 H MR spectrum of compound 3h Ph 13 C MR spectrum of compound 3h S-28

29 Ph Chiral HPLC chromatogram of compound 3h (racemic) Ph Chiral HPLC chromatogram of compound 3h S-29

30 p-clc 6 H 4 1 H MR spectrum of compound 3i p-clc 6 H 4 13 C MR spectrum of compound 3i S-30

31 p-clc 6 H 4 Chiral HPLC chromatogram of compound 3i (racemic) p-clc 6 H 4 Chiral HPLC chromatogram of compound 3i S-31

32 p-mec 6 H 4 1 H MR spectrum of compound 3j p-mec 6 H 4 13 C MR spectrum of compound 3j S-32

33 p-mec 6 H 4 Chiral HPLC chromatogram of compound 3j (racemic) p-mec 6 H 4 Chiral HPLC chromatogram of compound 3j S-33

34 1 H MR spectrum of compound 3k 13 C MR spectrum of compound 3k S-34

35 Chiral HPLC chromatogram of compound 3k (racemic) Chiral HPLC chromatogram of compound 3k S-35

36 1 H MR spectrum of compound 3l 13 C MR spectrum of compound 3l S-36

37 Chiral HPLC chromatogram of compound 3l (racemic) Chiral HPLC chromatogram of compound 3l S-37

38 1 H MR spectrum of compound 3m 13 C MR spectrum of compound 3m S-38

39 Chiral HPLC chromatogram of compound 3m (racemic) Chiral HPLC chromatogram of compound 3m S-39

40 1 H MR spectrum of compound 3n 13 C MR spectrum of compound 3n S-40

41 Chiral HPLC chromatogram of compound 3n (racemic) Chiral HPLC chromatogram of compound 3n S-41