Diastereoselective Synthesis of β-heteroaryl syn-α-methyl-β- Amino Acid Derivatives via a Double Chiral Auxiliary Approach.

Transcription

1 Supporting Information Diastereoselective Synthesis of β-heteroaryl syn-α-methyl-β- Amino Acid Derivatives via a Double Chiral Auxiliary Approach Jianwei Bian, * David Blakemore, Joseph S. Warmus, Jianmin Sun, Matthew Corbett, Colin R. Rose, and Bruce M. Bechle eusentis Chemistry, Pfizer Global Research and Development, Groton, CT 06340, USA and The Portway Building, Granta Park, Cambridge, CB21 6GS, UK Contents Materials and methods Experimental part MR spectra X-ray data for compound 3p S1 S2 S27 S79 Materials and methods General Procedures: All reactions were carried out under a nitrogen atmosphere with dry solvent under anhydrous conditions, unless otherwise noted. Solvents and Chemicals: All chemicals, reagents and solvents were purchased from commercial sources when available and used without further purification. (S)-4-benzyl- 5,5-dimethyloxazolidin-2-one was purchased from ECA International Corporation (ECA#: S16020). The starting aldehydes for making 1g, 1h, 1l, 1n, 1o, 1p, 1q, 1u and 1v were obtained from Pfizer internal sample bank. Data Collection: Proton ( 1 H MR) and carbon ( 13 C MR) nuclear magnetic spectroscopy were recorded with 400 and 500 MHz Bruker spectrometers. Chemical shifts are expressed in parts per million downfield from tetramethylsilane. The peak shapes are denoted as follows: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; br s, broad singlet. Mass spectrometry (MS) was performed via atmospheric pressure S1

2 chemical ionization (APCI) or electron scatter (ES) ionization sources. High resolution mass spectroscopy (HRMS) was performed on an Agilent (6220) LC-MS TOF using a Xbridge C µm 3.0 X 5.0 mm at 60 C; ammonium formate: water as mobile phase A1 and 50:50 Methanol:Acetonitrile as mobile Phase B1. Liquid chromatography mass spectrometry (LCMS) was performed on an Agilent 1100 Series (Waters Atlantis C18 column, 4.6 x 50 mm, 5 µm; 95% water/acetonitrile linear gradient to 5% water/acetonitrile over 4 min, hold at 5% water / 95% acetonitrile to 5.0 min, trifluoroacetic acid modifier (0.05%); flow rate of 2.0 ml/ min). Preparative HPLC purification was performed on a Waters FractionLynx preparative chromatography system using either a Phenomenex Gemini/Luna(2) C18 5µm 150 x 21.2 mm 5µ or Princeton Silica 5µm 250 x 21.2mm at 28 ml/min at nm detection. Column chromatography was performed with a Combiflash Companion from Teledyne Isco ; Redisep Rf silica (from Teledyne Isco ) under low nitrogen pressure were used. Whatman pre-coated silica gel plates (250 µm) were used for analytical TLC. Optical rotations were obtained on a Perkin Elmer Model 343 polarimeter at 20 C and 589 nm. Experimental part General procedure for the preparation of the heteroaryl tert-butanesulfinyl aldimines (1a-1w and 1y 1 ) Cs 2 CO 3 (1.2 equiv) was added to the mixture of the aldehyde (1 equiv) and (R)-(+)-tertbutanesulfinamide (1 equiv) in DCM (0.3 M). The mixture was stirred at room temperature overnight. The mixture was diluted with DCM and washed with H 2 O, dried over a 2 SO 4 and concentrated. The crude was purified by CombiFlash (12 g silica gel, EtOAc/heptane: 0 30%), leading to the desired product as an oil or solid. S2

3 General procedure for the SuperQuat enolate addition to the heteroaryl tertbutanesulfinyl aldimines (3a-3w and 3y 2 ) At -78 C, ahmds (0.39 ml, 1 M in THF, 0.39 mmol) was added dropwise to a solution of the SuperQuat (93.6 mg, 0.36 mmol) in THF (0.5 ml) over 4-5 minutes. The solution was stirred at -78 C for 1 h. The heteroaryl tert-butanesulfinyl aldimine (0.30 mmol) in THF (0.6 ml) was added dropwise over 5-6 minutes. The mixture was stirred at -78 C for 3 h. Quenched with sat. H 4 Cl (1 ml) followed by H 2 O (1 ml) and EtOAc (3 ml) at -78 C. The mixture was warmed up to rt and extracted with EtOAc (5 ml x 3). The combined organic layers were dried over a 2 SO 4 and concentrated. Purified by CombiFlash (4 g silica gel, EtOAc/heptane: 5 50%), leading to the desired product as a white solid. When the product was relatively less polar, a shallow gradient was applied in order to remove the intermediate A generated during the reaction, especially for lowyielding reactions. The major diastereomer 3t was inseparable from other diastereomers. Therefore the characterization data were not provided. 1 Using (S)-2-methylpropane-2-sulfinamide. 2 Using 1y (S,E)-2-methyl--((1-methyl-1H-benzo[d]imidazol-2-yl)methylene)propane-2-sulfinamide as the starting material. S3

4 O O O Bn (S)-2f (S)-4-benzyl-5,5-dimethyl-3-propionyloxazolidin-2-one ((S)-2f): At -78 C, nbuli (1.15 ml, 2.87 mmol, 2.5 M in hexane) was added to the solution of (S)-4- benzyl-5,5-dimethyloxazolidin-2-one (513 mg, 2.50 mmol) in THF (8 ml). The mixture was stirred for 20 minutes. CH 3 CH 2 COCl (0.44 ml, 5.0 mmol) was added. The mixture was stirred at -78 C for 30 minutes. The mixture was warmed up to rt and stirred for 1 h. The mixture was quenched with H 4 Cl (sat aq) and extracted with EtOAc twice. The combined organic layers were dried over a 2 SO 4 and concentrated. The crude material was purified by CombiFlash (12 g silica gel, EtOAc/heptane: 0 25%), leading to (S)-2f (620 mg, 94.9%) as a white solid. 1 H MR (400 MHz, CDCl 3 ) δ ppm (m, 5 H), 4.52 (dd, J=9.51, 3.90 Hz, 1 H), 3.17 (dd, J=14.15, 3.90 Hz, 1 H), (m, 3 H), 1.39 (s, 3 H), 1.38 (s, 3 H), 1.16 (t, J=7.32 Hz, 3 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 174.2, 152.6, 136.9, 129.0, 128.5, 126.7, 82.0, 63.4, 35.3, 29.2, 28.5, 22.2, 8.3. HRMS (ESI-TOF) calcd for C 15 H 20 O 3 [M+H] , found [α] 20 D = (c 0.39, CH 2 Cl 2 ). (R,E)-2-methyl--(pyridin-2-ylmethylene)propane-2-sulfinamide (1a): Yield: 98% as an oil. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.73 (d, J=4.15 Hz, 1 H), 8.69 (s, 1 H), 8.01 (d, J=7.81 Hz, 1 H), 7.80 (m, 1 H), 7.39 (m, 1 H), 1.27 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 163.9, 152.7, 150.4, 136.9, 126.1, 123.2, 58.2, HRMS (ESI-TOF) calcd for C 10 H 15 2 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S4

5 (R,E)--((6-chloropyridin-2-yl)methylene)-2-methylpropane-2- sulfinamide (1b): Yield: 71% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.65 (s, 1 H), 7.97 (dd, J=7.68, 0.85 Hz, 1 H), 7.79 (t, J=7.81 Hz, 1 H), 7.45 (dd, J=7.81, 0.73 Hz, 1 H), 1.28 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 162.6, 153.1, 152.0, 139.5, 126.9, 121.3, 58.5, HRMS (ESI-TOF) calcd for C 10 H 14 Cl 2 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R,E)-2-methyl--((6-methylpyridin-2-yl)methylene)propane-2- sulfinamide (1c): Yield: 93% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.69 (s, 1 H), 7.85 (d, J=7.56 Hz, 1 H), (m, 1 H), 7.27 (m, 1 H), 2.64 (s, 3 H), 1.29 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 164.2, 159.3, 152.2, 137.1, 125.8, 120.3, 58.2, 24.6, HRMS (ESI-TOF) calcd for C 11 H 17 2 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S O H F 1d (R,E)--((5-fluoropyridin-2-yl)methylene)-2-methylpropane-2- sulfinamide (1d): Yield: 98% as an oil. 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.68 (s, 1 H), 8.59 (d, J=2.73 Hz, 1 H), 8.08 (dd, J=8.78, 4.49 Hz, 1 H), (m, 1 H), 1.29 (s, 9 H). 13 C MR (101 MHz, CDCl 3 ) δ ppm 162.3, ( 1 J CF 263 Hz), ( 4 J CF 4.0 Hz), ( 2 J CF 24.6 Hz), ( 3 J CF 5.4 Hz), ( 2 J CF 18.7 Hz), 58.1, HRMS (ESI-TOF) calcd for C 10 H 14 F 2 OS [M+H] , found [α] 20 D = (c 1.48, CHCl 3 ). S5

6 Br S O H 1e (R,E)--((5-bromopyridin-2-yl)methylene)-2-methylpropane-2- S O H S O H sulfinamide (1e): Yield: 97% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.78 (dd, J=2.20, 0.73 Hz, 1 H) 8.64 (s, 1 H), (m, 2 H), 1.27 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 162.9, 151.5, 151.1, 139.7, 124.1, 123.9, 58.4, HRMS (ESI- TOF) calcd for C 10 H 14 Br 2 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). 1f Cl (R,E)--((4-chloropyridin-2-yl)methylene)-2-methylpropane-2- sulfinamide (1f): Yield: 88% as an oil. 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.68 (s, 1 H), 8.64 (d, J=5.46 Hz, 1 H), 8.02 (d, J=1.95 Hz, 1 H), 7.41 (dd, J=5.07, 1.95 Hz, 1 H), 1.29 (s, 9 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 162.7, 153.8, 150.9, 145.1, 125.9, 123.0, 58.3, HRMS (ESI-TOF) calcd for C 10 H 14 Cl 2 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). O 1g O (R,E)--((2,3-dihydro-[1,4]dioxino[2,3-c]pyridin-7-yl)methylene)- 2-methylpropane-2-sulfinamide (1g): Yield: 66% as a solid. 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.57 (s, 1 H), 8.29 (s, 1 H), 7.55 (s, 1 H), 4.38 (d, J=1.95 Hz, 4 H), 1.27 (s, 9 H). 13 C MR (101 MHz, CDCl 3 ) δ ppm 162.8, 150.0, 146.8, 143.2, 139.9, 112.0, 64.8, S6

7 64.3, 57.8, HRMS (ESI-TOF) calcd for C 12 H 17 2 O 3 S [M+H] , found [α] D 20 = (c 0.93, CHCl 3 ). S O H OBn 1h (R,E)--((3-(benzyloxy)pyridin-2-yl)methylene)-2-methylpropane-2- sulfinamide (1h): Yield: 88% as an oil. 1 H MR (500 MHz, CDCl 3 ) δ ppm 9.16 (s, 1 H), 8.40 (dd, J=4.27, 1.34 Hz, 1 H), (m, 7 H), 5.23 (d, J=3.66 Hz, 2 H), 1.28 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 158.9, 156.0, 142.8, 141.3, 135.6, 129.0, 128.6, 127.4, 127.1, 121.3, 70.9, 58.2, HRMS (ESI-TOF) calcd for C 17 H 21 2 O 2 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S O H Cl sulfinamide (1i): Yield: 90% as an oil. 1 H MR (500 MHz, CDCl 3 ) δ ppm 9.07 (s, 1 H), 8.71 (dd, J=4.39, 1.46 Hz, 1 H), 7.83 (dd, J=8.17, 1.59 Hz, 1 H), (m, 1 H), 1.32 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 159.7, 148.7, 148.2, 138.8, 134.5, 126.6, 58.6, HRMS (ESI-TOF) calcd for C 10 H 14 Cl 2 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). 1i (R,E)--((3-chloropyridin-2-yl)methylene)-2-methylpropane-2- S O H F 1j (R,E)--((3-fluoropyridin-2-yl)methylene)-2-methylpropane-2- sulfinamide (1j): Yield: 89% as an oil. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.87 (s, 1 H), 8.59 (d, J=4.39 Hz, 1 H), 7.54 (m, 1 H), (m, 1 H), 1.28 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm ( 1 J CF 268 Hz), ( 4 J CF 2.5 Hz), ( 3 J CF 5 Hz), S7

8 ( 2 J CF 7.5 Hz), ( 3 J CF 5 Hz), ( 2 J CF 18.7 Hz), 58.5, HRMS (ESI-TOF) calcd for C 10 H 14 F 2 OS [M+H] , found [α] D 20 = (c 1.0, CHCl 3 ). (R,E)-2-methyl--(quinolin-2-ylmethylene)propane-2-sulfinamide (1k): Yield: 83% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.88 (s, 1 H), 8.24 (d, J=8.54 Hz, 1 H), 8.19 (d, J=8.54 Hz, 1 H), 8.15 (d, J=8.29 Hz, 1 H), (m, 1 H), 7.77 (m, 1 H), 7.62 (m, 1 H), 1.31 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 164.4, 152.7, 148.2, 137.0, , , 129.1, 128.5, 127.9, 119.1, 58.4, HRMS (ESI- TOF) calcd for C 14 H 17 2 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S O H 1l (R,E)-2-methyl--(quinolin-8-ylmethylene)propane-2-sulfinamide (1l): Yield: 83% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm (s, 1 H), 9.02 (dd, J=4.15, 1.71 Hz, 1 H), 8.48 (dd, J=7.32, 1.46 Hz, 1 H), 8.21 (dd, J=8.29, 1.71 Hz, 1 H), 8.01 (dd, J=8.05, 1.46 Hz, 1 H), 7.66 (m, 1 H), 7.49 (dd, J=8.29, 4.15 Hz, 1 H), 1.33 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 161.2, 151.0, 146.8, 136.2, 132.4, 131.4, 128.7, 128.5, 126.4, 121.9, 58.0, HRMS (ESI-TOF) calcd for C 14 H 17 2 OS [M+H] , found [α] D 20 = (c 1.0, CHCl 3 ). S8

9 MeO S O H 1m OMe methylpropane-2-sulfinamide (1m): Yield: 51% as an oil. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.49 (s, 1 H), 6.07 (s, 1 H), 3.98 (s, 6 H), 1.28 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 171.9, 162.6, 159.3, 91.6, 58.6, 54.5, HRMS (ESI-TOF) calcd for C 11 H 18 3 O 3 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R,E)--((4,6-dimethoxypyrimidin-2-yl)methylene)-2- (R,E)-2-methyl--((2-methylpyrimidin-4-yl)methylene)propane- 2-sulfinamide (1n): Yield: 81% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.73 (m, 1 H) (m, 1 H) 7.66 (m, 1 H) 2.73 (d, J=1.95 Hz, 3 H) 1.21 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 169.0, 162.8, 158.3, 158.0, 115.1, 58.4, 25.7, HRMS (ESI-TOF) calcd for C 10 H 16 3 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S O H 1o (R,E)--(cinnolin-3-ylmethylene)-2-methylpropane-2-sulfinamide (1o): Yield: 81% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 9.34 (s, 1 H), 8.65 (d, J=9.03 Hz, 1 H), 8.58 (s, 1 H), (m, 2 H), 7.86 (m, 1 H), 1.35 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 162.7, 151.4, 149.6, 132.6, 132.1, 130.3, 128.0, 125.9, 122.4, 58.6, HRMS (ESI-TOF) calcd for C 13 H 16 3 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S9

10 S O H 1p (R,E)-2-methyl--(pyrazin-2-ylmethylene)propane-2-sulfinamide (1p): Yield: 72% as an oil. 1 H MR (500 MHz, CDCl 3 ) δ ppm 9.22 (d, J=1.46 Hz, 1 H), 8.71 (s, 1 H), 8.68 (dd, J=2.44, 1.46 Hz, 1 H), 8.64 (d, J=2.44 Hz, 1 H), 1.27 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 162.0, 147.8, 146.5, 144.9, 144.7, 58.7, HRMS (ESI-TOF) calcd for C 9 H 14 3 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). O S O S O H 1q ylsulfonyl)phenyl)pyrazin-2-yl)methylene)propane-2-sulfinamide (1q): Yield: 91% as a solid. 1 H MR (400 MHz, CDCl 3 ) δ ppm 9.25 (s, 1 H), 8.94 (s, 1 H), 8.82 (s, 1 H), 8.10 (d, J=7.81 Hz, 1 H), 7.69 (m, 2 H), 7.49 (dd, J=7.41, 1.17 Hz, 1 H), 3.11 (m, 4 H), 1.76 (m, 4 H), 1.34 (s, 9 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 161.7, 155.4, , , 142.8, 137.6, 136.4, 132.5, 132.2, 129.8, 129.5, 58.6, 47.2, 25.4, HRMS (ESI-TOF) calcd for C 19 H 25 4 O 3 S 2 [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R,E)-2-methyl--((5-(2-(pyrrolidin-1- S O H 1r (R,E)-2-methyl--((1-methyl-1H-benzo[d]imidazol-2- yl)methylene)propane-2-sulfinamide (1r): Yield: 98% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.85 (s, 1 H), 7.89 (d, J=8.29 Hz, 1 H), (m, 2 H), (m, 1 H), 4.18 (s, 3 H), 1.31 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 155.5, 146.1, S10

11 143.2, 137.2, 125.9, 123.8, 121.8, 110.3, 58.3, 32.2, HRMS (ESI-TOF) calcd for C 13 H 18 3 OS [M+H] , found [α] D 20 = (c 1.0, CHCl 3 ). S O H S 1s (R,E)-2-methyl--(thiazol-2-ylmethylene)propane-2-sulfinamide (1s): Yield: 96% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.81 (d, J=0.98 Hz, 1 H), 8.06 (d, J=3.17 Hz, 1 H), 7.60 (dd, J=2.93, 0.98 Hz, 1 H), 1.30 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 164.4, 156.6, 145.5, 124.3, 58.8, HRMS (ESI-TOF) calcd for C 8 H 13 2 OS 2 [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S O H S 1t (R,E)-2-methyl--(thiazol-4-ylmethylene)propane-2-sulfinamide (1t): Yield: 90% as a solid. 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.92 (d, J=1.95 Hz, 1 H), 8.72 (s, 1 H), 8.02 (d, J=1.95 Hz, 1 H), 1.26 (s, 9 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 155.6, 154.1, 152.7, 124.8, 57.8, HRMS (ESI-TOF) calcd for C 8 H 13 2 OS 2 [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S O H 1u (R,E)-2-methyl--((1-methyl-1H-pyrazol-3-yl)methylene)propane-2- sulfinamide (1u): Yield: 85% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.54 (s, 1 H), 7.35 (d, J=2.20 Hz, 1 H), 6.69 (d, J=2.20 Hz, 1 H), 3.90 (s, 3 H), 1.16 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 156.6, 148.8, 132.0, 106.6, 57.6, 39.6, HRMS (ESI-TOF) calcd for C 9 H 16 3 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S11

12 S O H 1y S O H 1v Bn (R,E)--((4-benzyl-4H-1,2,4-triazol-3-yl)methylene)-2-methylpropane- 2-sulfinamide (1v): Yield: 77% as a solid. 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.78 (s, 1 H), 8.27 (s, 1 H), (m, 3 H), 6.99 (d, J=6.63 Hz, 2 H), (m, 2 H), 1.03 (s, 9 H). 13 C MR (100 MHz, CDCl 3 ) d ppm 152.1, 149.0, 146.7, 134.5, 129.1, 128.4, 126.5, 58.0, 49.4, HRMS (ESI-TOF) calcd for C 14 H 19 4 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R,E)--((3-(4-cyanophenyl)-1-methyl-1H-1,2,4-triazol- 5-yl)methylene)-2-methylpropane-2-sulfinamide (1w): Yield: 70% as a solid. 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.68 (s, 1 H), 8.14 (d, J=8.20 Hz, 2 H), 7.65 (d, J=8.59 Hz, 2 H), 4.23 (s, 3 H), 1.26 (s, 9 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 160.0, 151.4, 149.1, 134.2, 132.2, 126.5, 118.4, 112.6, 58.2, 38.4, HRMS (ESI-TOF) calcd for C 15 H 18 5 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (S,E)-2-methyl--((1-methyl-1H-benzo[d]imidazol-2- yl)methylene)propane-2-sulfinamide (1y): Yield: 98% as a solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.85 (s, 1 H), 7.89 (d, J=8.29 Hz, 1 H), (m, 2 H), (m, 1 H), 4.18 (s, 3 H), 1.31 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 155.5, 146.1, 143.2, 137.2, 125.9, 123.8, 121.8, 110.3, 58.3, 32.2, HRMS (ESI-TOF) calcd for C 13 H 18 3 OS [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S12

13 (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2-oxooxazolidin-3- yl)-2-methyl-3-oxo-1-(pyridin-2-yl)propyl)-2-methylpropane-2-sulfinamide (3a): 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.50 (d, J=4.64 Hz, 1 H), (m, 2 H), (m, 5 H), (m, 1 H), 5.47 (d, J=7.07 Hz, 1 H), 5.10 (dd, J=7.07, 4.88 Hz, 1 H), 4.50 (dd, J=10.86, 2.32 Hz, 1 H), 4.19 (m, 1 H), 3.16 (d, J=14.15 Hz, 1 H), 2.74 (dd, J=14.64, Hz, 1 H), 1.34 (s, 3 H), 1.30 (s, 3 H), 1.26 (s, 9 H), 1.08 (d, J=6.83 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.6, 159.0, 152.7, 148.4, 137.4, 137.1, 129.0, 128.9, 126.9, 122.9, 122.8, 82.3, 64.3, 60.7, 56.8, 45.7, 34.9, 29.1, 23.3, 22.8, HRMS (ESI-TOF) calcd for C 25 H 34 3 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-1-(6-chloropyridin-2-yl)-2-methyl-3-oxopropyl)-2- methylpropane-2-sulfinamide (3b): 1 H MR (500 MHz, CDCl 3 ) δ ppm (m, 2 H), (m, 6 H), 5.01 (dd, J=7.93, 5.98 Hz, 1 H), 4.91 (d, J=8.05 Hz, 1 H), 4.48 (dd, J=10.98, 2.44 Hz, 1 H), 4.26 (m, 1 H), (m, 1 H), 2.74 (dd, J=14.64, Hz, 1 H), 1.34 (s, 3 H), 1.31 (s, 3 H), 1.26 (s, 9 H), 1.18 (d, J=6.83 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.7, 160.5, 152.6, 150.4, 139.8, 137.3, 129.0, 128.9, 126.9, 123.4, 121.8, 82.4, 64.2, 61.2, 56.9, 45.0, 34.7, 29.1, 23.2, 22.8, HRMS (ESI-TOF) calcd for C 25 H 33 Cl 3 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S13

14 (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-2-methyl-1-(6-methylpyridin-2-yl)-3-oxopropyl)-2- methylpropane-2-sulfinamide (3c): 1 H MR (500 MHz, CDCl 3 ) δ ppm (m, 1 H), (m, 1 H), (m, 5 H), 7.00 (d, J=7.56 Hz, 1 H), 5.71 (d, J=6.59 Hz, 1 H), 5.06 (dd, J=6.71, 4.76 Hz, 1 H), 4.50 (dd, J=10.98, 2.20 Hz, 1 H), (m, 1 H), (m, 1 H), 2.73 (dd, J=14.64, Hz, 1 H), 2.51 (s, 3 H), 1.33 (s, 3 H), 1.29 (s, 3 H), 1.26 (s, 9 H), 1.06 (d, J=6.83 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.8, 158.0, 157.0, 152.7, 137.4, 137.3, 129.0, 128.9, 126.9, 122.1, 119.7, 82.3, 64.3, 60.1, 56.7, 45.6, 34.9, 29.1, 24.6, 23.3, 22.9, HRMS (ESI-TOF) calcd for C 26 H 36 3 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-1-(5-fluoropyridin-2-yl)-2-methyl-3-oxopropyl)-2- methylpropane-2-sulfinamide (3d): 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.36 (d, J=2.68 Hz, 1 H), 7.69 (dd, J=8.54, 4.39 Hz, 1 H), 7.38 (m, 1 H), (m, 5 H), 5.18 (d, J=7.56 Hz, 1 H), (m, 1 H), 4.51 (dd, J=10.98, 2.44 Hz, 1 H), 4.18 (m, 1 H), (m, 1 H), 2.76 (dd, J=14.64, Hz, 1 H), 1.35 (s, 3 H), 1.32 (s, 3 H), 1.26 (s, 9 H), 1.11 (d, J=6.83 Hz, 3H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.5, ( 1 J CF 255 Hz), ( 4 J CF 3.7 Hz), 152.7, 137.2, ( 2 J CF 23.7 Hz), , , 127.0, ( 2 J CF 18.7 Hz), ( 3 J CF 5 Hz), 82.5, 64.3, 60.6, 56.8, 45.6, 34.9, 29.1, 23.2, 22.8, HRMS (ESI-TOF) calcd for C 25 H 33 F 3 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S14

15 (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-1-(5-bromopyridin-2-yl)-2-methyl-3-oxopropyl)-2- methylpropane-2-sulfinamide (3e): 1 H MR (500 MHz, CDCl 3 d) δ ppm 8.58 (d, J=2.20 Hz, 1 H), 7.78 (dd, J=8.42, 2.32 Hz, 1 H), 7.59 (d, J=8.54 Hz, 1 H), (m, 5 H), 5.18 (d, J=7.81 Hz, 1 H), 5.04 (dd, J=7.56, 5.12 Hz, 1 H), 4.51 (dd, J=10.86, 2.56 Hz, 1 H), 4.17 (m, 1 H), (m, 1 H), 2.75 (dd, J=14.64, Hz, 1 H), 1.35 (s, 3 H), 1.32 (s, 3 H), 1.26 (s, 9 H), 1.12 (d, J=6.83 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.4, 157.9, 152.7, 149.6, 139.7, 137.2, , , 127.0, 124.3, 119.9, 82.5, 64.2, 60.7, 56.8, 45.4, 34.9, 29.1, 23.2, 22.8, HRMS (ESI-TOF) calcd for C 25 H 33 Br 3 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2-oxooxazolidin-3- yl)-1-(4-chloropyridin-2-yl)-2-methyl-3-oxopropyl)-2-methylpropane-2-sulfinamide (3f): 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.41 (d, J=5.46 Hz, 1 H), 7.71 (d, J=1.56 Hz, 1 H), (m, 6 H), 5.37 (d, J=7.41 Hz, 1 H), 5.06 (dd, J=7.41, 5.07 Hz, 1 H), 4.51 (dd, J=10.93, 2.34 Hz, 1 H), 4.15 (m, 1 H), 3.17 (d, J=13.27 Hz, 1 H), 2.76 (dd, J=14.44, Hz, 1 H), 1.34 (s, 3 H), 1.31 (s, 3 H), 1.25 (s, 9 H), 1.09 (d, J=7.02 Hz, 3 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 174.1, 160.6, 152.5, 149.0, 144.9, 137.0, , , 126.8, 123.1, 123.0, 82.3, 64.1, 60.4, 56.6, 45.4, 34.7, 28.9, 23.0, 22.6, HRMS (ESI-TOF) calcd for C 25 H 33 Cl 3 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S15

16 O S H O O O OBn 3h Bn (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-1-(2,3-dihydro-[1,4]dioxino[2,3-c]pyridin-7-yl)-2-methyl-3- oxopropyl)-2-methylpropane-2-sulfinamide (3g): 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.05 (s, 1 H), 7.27 (m, 5 H), 7.15 (s, 1 H), (m, 1 H), 4.91 (dd, J=7.41, 5.46 Hz, 1 H), 4.49 (dd, J=10.73, 2.15 Hz, 1 H), (m, 4 H), 4.16 (m, 1 H), 3.11 (d, J=14.05 Hz, 1 H), 2.73 (dd, J=14.83, Hz, 1 H), 1.34 (s, 3 H), 1.30 (s, 3 H), 1.25 (s, 9 H), 1.12 (d, J=6.63 Hz, 3 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 174.6, 152.5, 152.3, 150.3, 140.5, 137.6, 137.2, 128.8, 128.7, 126.6, 110.9, 82.0, 64.7, 63.98, 63.96, 60.3, 56.4, 45.4, 34.6, 28.8, 23.0, 22.5, HRMS (ESI-TOF) calcd for C 27 H 36 3 O 6 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2-oxooxazolidin-3- yl)-1-(3-(benzyloxy)pyridin-2-yl)-2-methyl-3-oxopropyl)-2-methylpropane-2- sulfinamide (3h): 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.11 (dd, J=4.64, 1.22 Hz, 1 H), (m, 4 H), (m, 5 H), (m, 2 H), (m, 1 H), 5.35 (d, J=9.27 Hz, 1 H), 5.24 (dd, J=9.27, 6.34 Hz, 1 H), 5.13 (s, 2 H), (m, 1 H), 4.52 (dd, J=10.98, 2.20 Hz, 1 H), (m, 1 H), 2.82 (dd, J=14.64, Hz, 1 H), 1.32 (s, 3 H), 1.30 (s, 3 H), 1.28 (d, J=6.83 Hz, 3 H), 1.04 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 176.9, 152.6, 152.0, 149.8, 140.7, 138.2, 136.1, 129.3, 128.9, 128.8, 128.4, 127.5, 126.7, 123.4, 119.1, 82.1, 70.4, 64.6, 58.8, 56.3, 41.4, 34.5, 28.9, 22.69, 22.65, HRMS (ESI-TOF) calcd for C 32 H 40 3 O 5 S [M+H] , found [α] D 20 = (c 1.0, CHCl 3 ). S16

17 O S H O O O Cl Bn 3i yl)-1-(3-chloropyridin-2-yl)-2-methyl-3-oxopropyl)-2-methylpropane-2-sulfinamide (3i): 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.43 (dd, J=4.64, 1.46 Hz, 1 H), 7.62 (dd, J=8.05, 1.46 Hz, 1 H), (m, 6 H), 5.20 (dd, J=10.00, 8.54 Hz, 1 H), 4.56 (m, 1 H), 4.33 (dd, J=10.37, 2.81 Hz, 1 H), 4.26 (d, J=10.00 Hz, 1 H), (m, 1 H), 2.38 (dd, J=14.64, Hz, 1 H), 1.41 (d, J=6.83 Hz, 3 H), 1.25 (s, 6 H), 1.23 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 175.4, 158.2, 152.2, 147.4, 137.7, 136.9, 131.0, 129.0, 128.8, 127.0, 123.7, 82.1, 63.7, 59.6, 56.8, 44.2, 34.3, 28.8, 23.0, 22.5, HRMS (ESI-TOF) calcd for C 25 H 33 Cl 3 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2-oxooxazolidin-3- (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2-oxooxazolidin-3- yl)-1-(3-fluoropyridin-2-yl)-2-methyl-3-oxopropyl)-2-methylpropane-2-sulfinamide (3j): 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.34 (d, J=4.63 Hz, 1 H), (m, 1 H), (m, 2 H), (m, 2 H), 7.13 (d, J=7.56 Hz, 2 H), (m, 1 H), 4.52 (m, 1 H), 4.46 (d, J=9.76 Hz, 1 H), 4.36 (dd, J=10.49, 2.68 Hz, 1 H), 2.65 (d, J=2.20 Hz, 1 H), 2.46 (dd, J=14.39, Hz, 1 H), 1.36 (d, J=7.07 Hz, 3 H), 1.26 (s, 3 H), 1.25 (s, 3 H), 1.23 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 175.1, ( 1 J CF Hz), 152.2, ( 2 J CF 15 Hz), ( 4 J CF 6.25 Hz), 137.0, 129.0, 128.9, 126.9, ( 3 J CF 5 Hz), ( 2 J CF Hz), 82.1, 63.8, 56.86, 56.84, 43.9, 34.4, 28.9, 23.0, 22.6, HRMS (ESI-TOF) calcd for C 25 H 33 F 3 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S17

18 O S H O O O 3k Bn (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-2-methyl-3-oxo-1-(quinolin-2-yl)propyl)-2-methylpropane-2- sulfinamide (3k): 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.15 (d, J=8.54 Hz, 1 H), (m, 1 H), 7.86 (d, J=8.54 Hz, 1 H), 7.80 (d, J=8.05 Hz, 1 H), (m, 1 H), (m, 1 H), (m, 5 H), (m, 1 H), 5.33 (dd, J=6.34, 4.15 Hz, 1 H), 4.55 (dd, J=10.98, 2.44 Hz, 1 H), (m, 1 H), (m, 1 H), 2.74 (dd, J=14.64, Hz, 1 H), 1.36 (s, 3 H), (m, 12 H) 1.06 (d, J=6.59 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.6, 159.0, 152.9, 146.7, , , 129.7, 129.4, 129.0, 128.9, , , 126.9, 126.8, 120.6, 82.4, 64.4, 60.4, 59.9, 45.1, 34.8, 29.2, 23.3, 22.9, HRMS (ESI-TOF) calcd for C 29 H 36 3 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2-oxooxazolidin-3- yl)-2-methyl-3-oxo-1-(quinolin-8-yl)propyl)-2-methylpropane-2-sulfinamide (3l): 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.95 (dd, J=4.15, 1.71 Hz, 1 H), 8.17 (dd, J=8.29, 1.46 Hz, 1 H), 7.76 (dd, J=8.05, 1.22 Hz, 1 H), 7.62 (d, J=6.34 Hz, 1 H), (m, 2 H), (m, 5 H), 6.03 (d, J=9.27 Hz, 1 H), 5.51 (m, 1 H), (m, 1 H), 4.48 (dd, J=10.73, 1.95 Hz, 1 H), 3.48 (d, J=14.15 Hz, 1 H), 2.77 (dd, J=14.88, Hz, 1 H), 1.27 (s, 3 H), 1.26 (s, 3 H), 1.08 (d, J=6.83 Hz, 3 H), 1.00 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 177.3, 152.4, 149.7, 146.0, 138.7, 138.1, 136.6, 129.3, 129.0, , , 127.9, 126.6, 126.1, 121.5, 82.1, 64.7, 62.3, 59.9, 43.9, 34.8, 29.0, 22.7, 22.6, S18

19 17.1. HRMS (ESI-TOF) calcd for C 29 H 36 3 O 4 S [M+H] , found [α] D 20 = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-1-(4,6-dimethoxypyrimidin-2-yl)-2-methyl-3-oxopropyl)-2- methylpropane-2-sulfinamide (3m): 1 H MR (500 MHz, CDCl 3 ) δ ppm (m, 5 H), 5.90 (s, 1 H), 5.07 (d, J=7.07 Hz, 1 H), 4.94 (dd, J=7.07, 5.37 Hz, 1 H), 4.60 (m, 1 H), 4.49 (dd, J=10.86, 2.56 Hz, 1 H), 3.94 (s, 6 H), (m, 1 H), 2.73 (dd, J=14.64, Hz, 1 H), 1.32 (s, 3 H), 1.29 (s, 3 H), 1.26 (s, 9 H), 1.13 (d, J=7.07 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.9, 171.4, 167.4, 152.4, 137.4, 129.0, 128.9, 126.9, 88.8, 82.1, 64.3, 61.7, 56.6, 54.3, 43.8, 34.9, 29.0, 23.1, 22.8, HRMS (ESI- TOF) calcd for C 26 H 37 4 O 6 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-2-methyl-1-(2-methylpyrimidin-4-yl)-3-oxopropyl)-2- methylpropane-2-sulfinamide (3n): 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.55 (d, J=5.37 Hz, 1 H), 7.50 (d, J=5.37 Hz, 1 H), (m, 5 H), 5.40 (d, J=7.32 Hz, 1 H), 5.03 (dd, J=7.32, 4.88 Hz, 1 H), 4.50 (dd, J=10.73, 2.44 Hz, 1 H), 4.14 (m, 1 H), 3.14 (d, J=1.95 Hz, 1 H), 2.77 (dd, J=14.39, Hz, 1 H), 2.69 (s, 3 H), 1.34 (s, 3 H), 1.30 (s, 3 H), 1.25 (s, 9 H), 1.06 (d, J=6.83 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.0, 167.5, 167.3, 157.5, 152.7, 137.2, , , 127.0, 116.9, 82.6, 64.3, 59.8, 56.9, S19

20 45.0, 35.0, 29.1, 26.3, 23.2, 22.8, HRMS (ESI-TOF) calcd for C 25 H 35 4 O 4 S [M+H] , found [α] D 20 = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2-oxooxazolidin- 3-yl)-1-(cinnolin-3-yl)-2-methyl-3-oxopropyl)-2-methylpropane-2-sulfinamide (3o): 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.46 (dd, J=8.66, 0.85 Hz, 1 H), 8.20 (s, 1 H), (m, 2 H), (m, 1 H), (m, 2 H), (m, 3 H), 5.44 (d, J=8.54 Hz, 1 H), 5.35 (dd, J=8.29, 5.85 Hz, 1 H), (m, 2 H), 2.95 (d, J=2.20 Hz, 1 H), 2.62 (dd, J=14.64, Hz, 1 H), (m, 9 H), 1.27 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.6, 155.2, 152.7, 150.6, 137.1, 131.6, 130.9, 129.8, 128.9, 128.8, 127.3, 126.9, 126.7, 122.6, 82.5, 64.1, 61.3, 57.0, 45.9, 34.8, 29.1, 23.2, 22.7, HRMS (ESI-TOF) calcd for C 28 H 35 4 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). O S H O O O 3p Bn (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2-oxooxazolidin-3- yl)-2-methyl-3-oxo-1-(pyrazin-2-yl)propyl)-2-methylpropane-2-sulfinamide (3p): 1 H MR (500 MHz, CDCl 3 ) δ ppm 8.94 (s, 1 H), 8.47 (s, 2 H), (m, 5 H), 5.14 (dd, J=8.05, 5.37 Hz, 1 H), 5.05 (d, J=8.05 Hz, 1 H), 4.48 (dd, J=10.73, 2.44 Hz, 1 H), 4.20 (m, 1 H), (m, 1 H), 2.73 (dd, J=14.64, Hz, 1 H), 1.33 (s, 3 H), 1.31 (s, 3 H), 1.24 (s, 9 H), 1.14 (d, J=6.83 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.1, 155.1, 152.6, 145.0, 143.9, 143.1, 137.1, , , 127.0, 82.6, 64.2, 59.3, 56.9, 45.3, 34.9, 29.1, 23.1, 22.8, HRMS (ESI-TOF) calcd for C 24 H 33 4 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S20

21 O S O O S H O O O 3q Bn (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-2-methyl-3-oxo-1-(5-(2-(pyrrolidin-1-ylsulfonyl)phenyl)pyrazin- 2-yl)propyl)-2-methylpropane-2-sulfinamide (3q): 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.92 (d, J=1.17 Hz, 1 H), 8.73 (d, J=1.17 Hz, 1 H), 8.05 (dd, J=7.81, 1.17 Hz, 1 H), 7.60 (m, 2 H), 7.40 (dd, J=7.41, 1.56 Hz, 1 H), (m, 5 H), 5.17 (dd, J=8.00, 5.66 Hz, 1 H), 5.04 (d, J=8.20 Hz, 1 H), 4.50 (dd, J=10.93, 2.34 Hz, 1 H), (m, 1 H), 3.08 (d, J=14.44 Hz, 1 H), (m, 5 H), (m, 4 H), 1.33 (s, 3 H), 1.31 (s, 3 H), 1.26 (s, 9 H), 1.22 (d, J=6.63 Hz, 3 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 173.9, 153.1, 152.3, 144.1, 142.6, 137.3, 137.1, 136.7, 132.4, 132.3, 129.4, 129.2, 128.7, 128.6, 126.6, 82.2, 63.9, 59.0, 56.6, 46.9, 45.2, 34.6, 28.8, 25.2, 22.8, 22.5, HRMS (ESI-TOF) calcd for C 34 H 44 5 O 6 S 2 [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). O S H O O O 3r Bn (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-2-methyl-1-(1-methyl-1h-benzo[d]imidazol-2-yl)-3-oxopropyl)- 2-methylpropane-2-sulfinamide (3r): 1 H MR (500 MHz, CDCl 3 ) δ ppm (m, 1 H), (m, 3 H), (m, 3 H), (m, 2 H), 4.86 (t, J=9.15 Hz, 1 H), 4.64 (m, 1 H), 4.29 (dd, J=10.25, 3.42 Hz, 1 H), 4.23 (d, J=8.78 Hz, 1 H), 3.91 (s, 3 H), 2.47 (dd, J=14.88, 3.42 Hz, 1 H), 2.06 (dd, J=14.88, Hz, 1 H), 1.45 (d, J=6.83 Hz, 3 H), 1.24 (s, 9 H), 1.21 (s, 3 H), 1.20 (s, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 175.8, 154.6, 152.3, 142.3, 136.8, 135.7, 128.7, 128.6, 126.7, 123.0, 122.4, 119.6, 110.1, 82.4, 63.6, 57.1, 54.9, 45.2, 33.8, 30.1, 28.7, 23.1, 22.4, HRMS (ESI-TOF) calcd for C 28 H 36 4 ao 4 S [M+a] , found [α] 20 D = (c 1.0, CHCl 3 ). S21

22 S O H O O O S Bn 3s (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2-oxooxazolidin-3- yl)-2-methyl-3-oxo-1-(thiazol-2-yl)propyl)-2-methylpropane-2-sulfinamide (3s): 1 H O S H O O O 3u Bn MR (500 MHz, CDCl 3 ) δ ppm 7.65 (d, J=3.17 Hz, 1 H), (m, 6 H), 5.24 (dd, J=8.05, 6.10 Hz, 1 H), 4.65 (d, J=7.81 Hz, 1 H), 4.48 (dd, J=10.98, 2.44 Hz, 1 H), (m, 1 H), (m, 1 H), 2.75 (dd, J=14.64, Hz, 1 H), 1.33 (s, 3 H), 1.31 (s, 3 H), 1.24 (s, 9 H), 1.23 (d, J = 6.83 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 174.2, 169.9, 152.6, 141.8, 137.3, 129.0, 128.9, 126.9, 120.6, 82.5, 64.2, 59.2, 57.1, 45.8, 34.7, 29.1, 23.1, 22.7, HRMS (ESI-TOF) calcd for C 23 H 32 3 O 4 S 2 [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2-oxooxazolidin-3- yl)-2-methyl-1-(1-methyl-1h-pyrazol-3-yl)-3-oxopropyl)-2-methylpropane-2- sulfinamide (3u): 1 H MR (500 MHz, CDCl 3 ) δ ppm (m, 7 H), 6.13 (d, J=1.95 Hz, 1 H), 4.92 (d, J=8.29 Hz, 1 H), 4.66 (dd, J=8.05, 6.10 Hz, 1 H), (m, 2 H), 3.81 (s, 3 H), (m, 1 H), 2.81 (dd, J=14.88, Hz, 1 H), (m, 9 H), 1.18 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 176.7, 152.6, 152.4, 137.7, 130.9, 129.2, 128.8, 126.8, 104.4, 82.3, 64.2, 58.5, 56.2, 42.6, 39.0, 34.9, 28.9, 22.9, 22.5, HRMS (ESI-TOF) calcd for C 24 H 35 4 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S22

23 O S H Bn O O O Bn 3v (R)--((1R,2R)-1-(4-benzyl-4H-1,2,4-triazol-3-yl)-3-((S)-4- benzyl-5,5-dimethyl-2-oxooxazolidin-3-yl)-2-methyl-3-oxopropyl)-2-methylpropane- 2-sulfinamide (3v): 1 H MR (400 MHz, CDCl 3 ) δ ppm 7.69 (s, 1 H), (m, 10 H), (d, J=14.8 Hz, 1 H), (d, J=14.8 Hz, 1 H), (m, 2 H), 4.32 (dd, J=10.15, 2.73 Hz, 1 H), 4.17 (d, J=8.98 Hz, 1 H), 2.60 (dd, J=14.8, 10.2 Hz, 1 H), 2.51 (m, 1 H), (d, J=6.4 Hz, 3 H), 1.29 (s, 3 H), 1.26 (s, 3 H), 1.25 (s, 9 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 175.2, 155.0, 151.7, 143.5, 137.1, 134.0, 129.0, 128.7, 128.6, 128.4, 126.6, 82.1, 63.7, 57.0, 53.3, 48.3, 44.2, 34.1, 28.8, 22.8, 22.3, HRMS (ESI-TOF) calcd for C 29 H 38 5 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (R)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-1-(3-(4-cyanophenyl)-1-methyl-1h-1,2,4-triazol-5-yl)-2-methyl- 3-oxopropyl)-2-methylpropane-2-sulfinamide (3w): 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.13 (d, J=8.20 Hz, 2 H), 7.70 (d, J=8.20 Hz, 2 H), (m, 3 H), 6.93 (d, J=6.63 Hz, 2 H), (m, 1 H), (m, 1 H), 4.35 (dd, J=9.95, 3.32 Hz, 1 H), 4.04 (s, 3 H), 3.95 (d, J=9.76 Hz, 1 H), (m, 1 H), 2.37 (dd, J=14.44, Hz, 1 H), 1.45 (d, J=6.63 Hz, 3 H), 1.29 (s, 3 H), 1.26 (s, 9 H), 1.21 (s, 3 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 174.8, 158.7, 156.7, 151.9, 136.4, 135.1, 132.3, 128.5, 128.4, 126.6, 126.5, 118.8, 112.2, 82.3, 63.4, 56.9, 54.0, 44.2, 35.7, 34.1, 28.5, 22.7, 22.2, HRMS (ESI-TOF) calcd for C 30 H 37 6 O 4 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S23

24 (S)--((1R,2R)-3-((S)-4-benzyl-5,5-dimethyl-2- oxooxazolidin-3-yl)-2-methyl-1-(1-methyl-1h-benzo[d]imidazol-2-yl)-3-oxopropyl)- 2-methylpropane-2-sulfinamide (3y): 1 H MR (500 MHz, CDCl 3 ) d ppm (m, 1 H), (m, 3 H), (m, 3 H), (m, 2 H), 4.95 (t, J=9.15 Hz, 1 H), (m, 1 H), 4.31 (dd, J=10.12, 3.29 Hz, 1 H), (br s, 1 H), 3.83 (s, 3 H), 2.53 (dd, J=14.76, 3.05 Hz, 1 H), 2.21 (dd, J=14.88, Hz, 1 H), 1.59 (d, J=7.07 Hz, 3 H), 1.25 (s 3 H), 1.23 (s, 3 H), 1.14 (s, 9 H). 13 C MR (125 MHz, CDCl 3 ) d ppm 175.9, 154.3, 152.3, 142.2, 137.1, 135.6, 128.8, 128.6, 126.6, 123.0, 122.5, 119.8, 109.9, 82.3, 63.6, 57.0, 54.7, 44.2, 33.9, 30.2, 28.7, 22.6, 22.5, HRMS (ESI-TOF) calcd for C 28 H 36 4 ao 4 S [M+a] , found [α] 20 D = (c 1.0, CHCl 3 ). (S)-3-((2R,3R)-3-amino-2-methyl-3-(1-methyl-1Hbenzo[d]imidazol-2-yl)propanoyl)-4-benzyl-5,5-dimethyloxazolidin-2-one (4): 3r or 3y (122 mg, mmol) in MeOH (3 ml) was treated with HCl (0.3 ml, 4 in dioxane). The mixture was stirred at rt for 90 minutes.the solvent was removed. The residue was diluted with 40 ml EtOAc and washed with ahco3 (sat aq), dried over a2so4 and concentrated. The crude material was purified by CombiFlash (4 g silica gel, B/A: 0 50%; A:DCM, B:10% MeOH in DCM), leading to 4 (93.4 mg, 95%) as a white solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm (m, 1 H), (m, 6 H), 7.10 (d, J=7.32 Hz, 2 H), 4.51 (d, J=7.32 Hz, 1 H), 4.46 (dd, J=10.25, 3.42 Hz, 1 H), 4.39 (m, 1 H), 3.86 (s, 3 H), 2.93 (dd, J=14.76, 3.29 Hz, 1 H), 2.52 (dd, J=14.88, Hz, 1 H), 1.86 (br. s., 2 H), 1.33 (d, J=6.83 Hz, 3 H), 1.31 (s, 3 H), 1.30 (s, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 176.0, 156.1, 152.7, 142.2, 137.2, 136.2, 129.0, 128.7, 126.8, 122.6, 122.1, 119.6, 109.5, 82.4, 63.7, 50.8, 44.1, 34.4, 30.1, 28.8, 22.6, HRMS (ESI- S24

25 TOF) calcd for C 24 H 29 4 O 3 [M+H] , found [α] D 20 = (c 1.0, CHCl 3 ). (2R,3R)-methyl-3-amino-2-methyl-3-(1-methyl-1Hbenzo[d]imidazol-2-yl)propanoate (5): 2 H 3 in MeOH (5.20 ml) was added to the flask containing 4 (175 mg, mmol). The mixture was stirred at rt for 4 h. LCMS indicated the starting material was fully converted to the desired product. The solvent was removed. The crude material was purified by CombiFlash (4 g silica gel, B/A: 0 50%; A:DCM, B:10% MeOH in DCM), leading to 5 (95.4 mg, 93%) as a white solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm (m, 1 H), (m, 3 H), 4.46 (d, J=6.59 Hz, 1 H), 3.77 (s, 3 H), 3.60 (s, 3 H), (m, 1 H), 1.86 (br. s., 2 H), 1.31 (d, J=7.32 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 175.3, 156.5, 142.3, 136.0, 122.6, 122.1, 119.7, 109.4, 52.1, 50.2, 45.0, 30.0, HRMS (ESI-TOF) calcd for C 13 H 18 3 O 2 [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). (2R,3R)-methyl 3-((R)-1,1-dimethylethylsulfinamido)-2-methyl-3- (thiazol-2-yl)propanoate (6): Prepared with the same procedure as 5. The crude material was purified by CombiFlash (4 g silica gel, EtOAc/heptane: 0 70%), leading to the desired product (57.2 mg, 83%) as a crystalline solid. 1 H MR (500 MHz, CDCl 3 ) δ ppm 7.71 (d, J=3.42 Hz, 1 H), 7.30 (d, J=3.42 Hz, 1 H), 5.16 (dd, J=8.42, 5.25 Hz, 1 H), (d, J=8.42 Hz, 1 H), 3.67 (s, 3 H), 3.13 (m, 1 H), 1.23 (s, 9 H), 1.17 (d, J=7.07 Hz, 3 H). 13 C MR (125 MHz, CDCl 3 ) δ ppm 173.6, 170.0, 142.5, 120.0, 59.4, 56.8, 52.1, 46.5, 22.9, HRMS (ESI-TOF) calcd for C 12 H 21 2 O 3 S 2 [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S25

26 (2R,3R)-3-(4-chloropyridin-2-yl)-3-((R)-1,1- dimethylethylsulfinamido)-2-methylpropanamide (7): A solution of 3f (110 mg, mmol) in DMF (2 ml) was cooled to -30 C. H 3 (gas, Aldrich) was bubbled through until the volume was apparently increased (~0.3 ml). The clear solution was stirred in the sealed vial at rt for 3 days. A tiny needle was used to release the pressure until no bubbles formed. The solvent was removed under rotavap. The crude material was purified by CombiFlash (4 g silica gel, B/A: 0 50%; A:DCM, B:20% MeOH in DCM), leading to 7 (56 mg, 81%) as a white solid. 1 H MR (400 MHz, CDCl 3 ) δ ppm 8.38 (d, J=5.46 Hz, 1 H), 7.36 (d, J=1.95 Hz, 1 H), 7.16 (dd, J=5.27, 1.76 Hz, 1 H), (br s, 1 H), (br s, 1 H), 4.82 (d, J=8.59 Hz, 1 H), 4.58 (t, J=8.20 Hz, 1 H), 2.77 (m, 1 H), 1.22 (s, 9 H), (d, J=7.2 Hz, 3 H). 13 C MR (100 MHz, CDCl 3 ) δ ppm 175.9, 161.5, 149.8, 144.8, 123.4, 123.1, 62.9, 56.5, 47.1, 22.7, HRMS (ESI-TOF) calcd for C 13 H 21 Cl 3 O 2 S [M+H] , found [α] 20 D = (c 1.0, CHCl 3 ). S26

27 S27

28 S28

29 S29

30 S30

31 S31

32 S32

33 S33

34 S34

35 S35

36 S36

37 S37

38 S38

39 S39

40 S40

41 S41

42 S42

43 S43

44 S44

45 S45

46 S46

47 S47

48 S48

49 S49

50 S50

51 S51

52 S52

53 S53

54 S54

55 S55

56 S56

57 S57

58 S58

59 S59

60 S60

61 S61

62 S62

63 S63

64 S64

65 S65

66 S66

67 S67

68 S68

69 S69

70 S70

71 S71

72 S72

73 S73

74 S74

75 S75

76 S76

77 S77

78 S78

79 SUMMARY: The structure was solved in the P2(1) space group The asymmetric unit is comprised of one molecule of PF R value 5.5% Absolute configuration Figure 1. ORTEP with ellipsoids drawn at 50% confidence level. S79

80 EXPERIMETAL: Data collection was performed on a Bruker APEX diffractometer at room temperature. Data collection consisted of 3 omega scans and low angle and three at high angle; each with 0.5 step. In addition, 2 phi scans were collected to improve the quality of the absorption correction. The structure was solved by direct methods using SHELX software suite in the space group P2(1). The structure was subsequently refined by the full-matrix least squares method. All non-hydrogen atoms were found and refined using anisotropic displacement parameters. The hydrogen atom located on nitrogen was found from the Fourier difference map and refined with distance restrained. The remaining hydrogen atoms were placed in calculated positions and were allowed to ride on their carrier atoms. The final refinement included isotropic displacement parameters for all hydrogen atoms. Absolute configuration determined by examination of the Flack parameter; in this case the parameter is 0.06 with and esd of 0.04; within range for an enantiopure compound. The final R-index was 5.5%. A final difference Fourier revealed no missing or misplaced electron density. Pertinent crystal, data collection and refinement are summarized in table 1. Atomic coordinates, bond lengths, bond angles, Torsion angles and displacement parameters are listed in tables 2 6. Software and References SHELXTL, Version 5.1, Bruker AXS, 1997 PLATO, A.L. Spek, J. Appl. Cryst. 2003, 36, MERCURY, C.F. Macrae, P.R. Edington, P. McCabe, E. Pidcock, G.P. Shields, R. Taylor, M. Towler and J. van de Streek, J. Appl. Cryst. 39, , R.W.W. Hooft et al. J. Appl. Cryst. (2008) H.D. Flack, Acta Cryst. 1983, A39, S80

81 Table 8. Crystal data and structure refinement for PF Identification code z204 Empirical formula C24 H32 4 O4 S Formula weight Temperature 298(2) K Wavelength Å Crystal system Monoclinic Space group P2(1) Unit cell dimensions a = (4) Å α= 90. b = (18) Å β= (12). c = (4) Å γ = 90. Volume (6) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 504 Crystal size 0.21 x 0.15 x 0.1 mm 3 Theta range for data collection 2.84 to Index ranges -13<=h<=13, -5<=k<=6, -16<=l<=12 Reflections collected 4815 Independent reflections 2286 [R(int) = ] Completeness to theta = % Absorption correction Empirical Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2286 / 2 / 309 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.06(4) Extinction coefficient (7) Largest diff. peak and hole and e.å -3 S81

82 Table 9. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for PF U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) S(001) 915(1) 1363(3) 7547(1) 85(1) O(3) 4467(3) 1701(6) 9699(3) 78(1) O(4) 5283(3) 2810(7) 8748(3) 78(1) C(5) 2167(5) -181(10) 8977(4) 65(2) (4) 4151(4) 202(9) 8331(3) 70(1) C(4) 1810(5) -68(11) 9774(4) 67(2) C(13) 4597(5) 1565(10) 8996(4) 68(2) (2) 2073(5) 1091(10) 11210(4) 96(2) O(2) 3333(4) -2730(7) 7710(3) 100(2) (3) 1329(4) -650(9) 8214(3) 80(2) C(17) 4427(5) 787(9) 7536(3) 65(2) C(19) 3553(5) 2134(13) 6018(4) 81(2) C(10) 3051(5) -1827(9) 9082(4) 66(2) C(3) 2348(5) 950(11) 10495(4) 77(2) C(18) 3519(5) 1928(11) 6933(3) 77(2) C(14) 5422(5) 2066(10) 7927(4) 75(2) (1) 938(5) -1103(9) 9768(4) 90(2) O(1) 288(4) 2879(10) 7884(3) 134(2) C(24) 3389(7) 3984(16) 5603(6) 120(3) C(1) 665(6) -990(13) 10496(5) 100(2) C(12) 3526(5) -1596(11) 8338(5) 73(2) C(16) 5556(6) 4071(12) 7435(4) 96(2) C(22) 3579(8) 2420(30) 4328(6) 143(4) C(20) 3710(8) 434(16) 5567(5) 143(4) C(6) 3(7) -135(18) 6704(5) 126(3) C(11) 2680(6) -4107(9) 9123(5) 98(2) C(2) 1217(7) 50(14) 11212(5) 94(2) C(7) -776(8) -1290(20) 7020(7) 213(7) C(23) 3394(9) 4180(20) 4749(7) 150(4) C(15) 6371(5) 655(13) 8131(5) 106(3) C(9) -468(7) 1520(20) 6034(5) 187(5) C(21) 3717(10) 530(20) 4717(6) 176(5) C(8) 694(12) -1620(20) 6332(7) 226(6) S82

83 Table 10. Bond lengths [Å] and angles [ ] for PF S(001)-O(1) 1.472(5) S(001)-(3) 1.653(5) S(001)-C(6) 1.822(9) O(3)-C(13) 1.201(6) O(4)-C(13) 1.352(7) O(4)-C(14) 1.467(6) C(5)-(3) 1.453(7) C(5)-C(4) 1.496(7) C(5)-C(10) 1.549(8) (4)-C(13) 1.375(8) (4)-C(12) 1.409(8) (4)-C(17) 1.480(6) C(4)-(1) 1.338(7) C(4)-C(3) 1.351(8) (2)-C(3) 1.311(7) (2)-C(2) 1.323(8) O(2)-C(12) 1.208(7) C(17)-C(18) 1.513(8) C(17)-C(14) 1.538(8) C(19)-C(24) 1.328(10) C(19)-C(20) 1.341(10) C(19)-C(18) 1.499(8) C(10)-C(12) 1.516(8) C(10)-C(11) 1.523(8) C(14)-C(15) 1.512(9) C(14)-C(16) 1.526(9) (1)-C(1) 1.328(7) C(24)-C(23) 1.388(12) C(1)-C(2) 1.357(9) C(22)-C(21) 1.335(14) C(22)-C(23) 1.352(13) C(20)-C(21) 1.378(11) C(6)-C(7) 1.476(11) C(6)-C(9) 1.508(13) C(6)-C(8) 1.548(14) O(1)-S(001)-(3) 112.1(3) O(1)-S(001)-C(6) 105.9(4) (3)-S(001)-C(6) 97.4(4) C(13)-O(4)-C(14) 110.7(5) (3)-C(5)-C(4) 112.5(5) (3)-C(5)-C(10) 110.4(5) C(4)-C(5)-C(10) 110.9(5) C(13)-(4)-C(12) 128.6(6) Symmetry transformations used to generate equivalent atoms: C(13)-(4)-C(17) 111.4(5) C(12)-(4)-C(17) 119.9(5) (1)-C(4)-C(3) 119.7(6) (1)-C(4)-C(5) 117.4(6) C(3)-C(4)-C(5) 122.9(7) O(3)-C(13)-O(4) 122.1(6) O(3)-C(13)-(4) 129.7(7) O(4)-C(13)-(4) 108.2(5) C(3)-(2)-C(2) 115.3(6) C(5)-(3)-S(001) 116.2(4) (4)-C(17)-C(18) 109.0(4) (4)-C(17)-C(14) 99.8(4) C(18)-C(17)-C(14) 118.2(5) C(24)-C(19)-C(20) 116.7(7) C(24)-C(19)-C(18) 121.9(7) C(20)-C(19)-C(18) 121.4(7) C(12)-C(10)-C(11) 109.9(6) C(12)-C(10)-C(5) 109.1(5) C(11)-C(10)-C(5) 112.3(5) (2)-C(3)-C(4) 125.3(6) C(19)-C(18)-C(17) 115.9(5) O(4)-C(14)-C(15) 107.5(5) O(4)-C(14)-C(16) 105.8(5) C(15)-C(14)-C(16) 112.5(6) O(4)-C(14)-C(17) 102.9(4) C(15)-C(14)-C(17) 111.7(5) C(16)-C(14)-C(17) 115.5(5) C(1)-(1)-C(4) 115.1(6) C(19)-C(24)-C(23) 122.2(9) (1)-C(1)-C(2) 124.2(7) O(2)-C(12)-(4) 117.0(6) O(2)-C(12)-C(10) 124.8(6) (4)-C(12)-C(10) 117.8(6) C(21)-C(22)-C(23) 120.5(10) C(19)-C(20)-C(21) 123.6(10) C(7)-C(6)-C(9) 112.9(9) C(7)-C(6)-C(8) 113.6(11) C(9)-C(6)-C(8) 108.2(9) C(7)-C(6)-S(001) 112.9(6) C(9)-C(6)-S(001) 104.1(7) C(8)-C(6)-S(001) 104.4(6) (2)-C(2)-C(1) 120.3(7) C(22)-C(23)-C(24) 118.9(9) C(22)-C(21)-C(20) 118.0(10) S83

84 Table 11. Anisotropic displacement parameters (Å 2 x 10 3 ) for PF The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 S(001) 87(1) 107(1) 64(1) 10(1) 26(1) 8(1) O(3) 101(3) 77(3) 59(2) -11(2) 29(2) -9(3) O(4) 91(3) 80(3) 73(3) 0(2) 38(3) -12(3) C(5) 84(4) 54(4) 52(4) 3(3) 12(4) -5(4) (4) 85(4) 69(3) 62(3) -15(3) 29(3) -3(3) C(4) 80(5) 66(4) 55(4) 0(4) 19(4) 2(4) C(13) 85(5) 62(4) 57(4) 0(4) 21(4) 1(4) (2) 112(5) 113(5) 78(4) -18(4) 52(4) -23(4) O(2) 121(4) 83(3) 109(4) -39(3) 52(3) -28(3) (3) 97(4) 76(4) 62(3) -1(3) 12(3) -1(3) C(17) 89(5) 65(4) 48(3) -15(3) 31(4) 0(4) C(19) 84(5) 92(6) 66(4) 5(5) 19(4) 5(4) C(10) 80(4) 56(4) 66(4) 0(3) 26(4) 3(3) C(3) 92(5) 85(5) 65(4) -8(4) 40(4) -11(4) C(18) 85(4) 86(5) 62(4) -4(4) 22(4) 8(4) C(14) 92(5) 87(5) 54(4) -4(4) 35(4) -6(4) (1) 88(4) 104(4) 84(5) -3(4) 35(4) -17(4) O(1) 134(4) 147(5) 123(4) 3(4) 41(4) 63(4) C(24) 168(8) 104(7) 73(5) 15(5) 6(5) 11(6) C(1) 106(6) 125(6) 88(5) -8(5) 57(5) -24(5) C(12) 81(5) 58(5) 78(5) -11(4) 19(4) -1(4) C(16) 105(5) 110(6) 75(4) 13(4) 29(4) -12(5) C(22) 144(8) 211(13) 81(6) 22(10) 40(6) 11(9) C(20) 263(12) 104(7) 73(5) 5(5) 64(7) 35(7) C(6) 126(7) 176(9) 62(5) 7(6) 1(5) -13(7) C(11) 129(6) 52(4) 125(6) 1(4) 55(5) -4(4) C(2) 109(6) 103(5) 85(5) -3(5) 51(5) -1(5) C(7) 152(8) 307(17) 138(9) 75(10) -32(7) -136(11) C(23) 205(11) 115(8) 104(8) 38(7) 3(7) -4(8) C(15) 91(5) 121(6) 113(6) 4(5) 40(5) 30(5) C(9) 175(8) 259(13) 87(6) 73(8) -34(6) -47(10) C(21) 314(15) 147(10) 82(6) 18(7) 81(8) 56(10) C(8) 264(14) 266(16) 119(9) -113(10) 2(9) -26(13) S84

85 Table 12. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for PF x y z U(eq) H(004) H(011) H(013) H(014) H(01A) H(01B) H(019) H(020) H(02A) H(02B) H(02C) H(023) H(024) H(02D) H(02E) H(02F) H(027) H(02G) H(02H) H(02I) H(029) H(03A) H(03B) H(03C) H(2A) H(2B) H(2C) H(3) H(1A) H(1B) H(1C) H(99A) 770(50) -1430(120) 8380(50) 150(40) S85