SUPPORTING INFORMATION

Transcription

1 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2015 SUPPORTING INFORMATION Grignard-mediated reduction of 2,2,2-trichloro-1-arylethanones: One-pot reduction/aldol routes to 2,2-dichloro-3-hydroxy-1,3-diarylpropan-1-ones and related molecules Ali H. Essa, a,b Reinner I. Lerrick, a,c Eçe Çiftçi, a Ross W. Harrington, a Paul G. Waddell, a William Clegg a and Michael J. Hall* a a School of Chemistry, Newcastle University, Newcastle upon Tyne NE1 7RU, U.K., michael.hall@newcastle.ac.uk b Department of Chemistry, College of Science, University of Basrah, Basrah, Iraq. c School of Chemistry, Nusa Cendana University, Indonesia General experimental information Experimental procedures: 1d - 2,2,2-trichloro-1-(5-methylfuran-2-yl)ethan-1-one 1e - 2,2,2-trichloro-1-(1H-indol-3-yl)ethan-1-one 1f - 2,2,2-trichloro-1-(1-methyl-1H-indol-3-yl)ethan-1-one Crystal Data and Structure Refinement Tables: 1e - 2,2,2-trichloro-1-(1H-indol-3-yl)ethan-1-one 1f - 2,2,2-trichloro-1-(1-methyl-1H-indol-3-yl)ethan-1-one 2a - 2,2-dichloro-1-(1-methyl-1H-pyrrol-2-yl)ethan-1-one 2f - 2,2-dichloro-1-(1-methyl-1H-indol-3-yl)ethan-1-one 2h - 2,2-dichloro-3-hydroxy-3-(perfluorophenyl)-1-(p-tolyl)propan-1-one 2j - 2,2-dichloro-3-hydroxy-1-(1H-indol-3-yl)-3-(perfluorophenyl)propan-1-one 2k - 2,2-dichloro-3-hydroxy-1-(1-methyl-1H-indol-3-yl)-3- (perfluorophenyl)propan-1-one 2o - 2,2-dichloro-3-hydroxy-3-(4-nitrophenyl)-1-(p-tolyl)propan-1-one 2t - diethyl 2-(1,1-dichloro-2-(1-methyl-1H-indol-3-yl)-2-oxoethyl)-2- hydroxymalonate 3a - (1R*,3R*)-2,2-dichloro-3-hydroxy-3-(4-nitrophenyl)-1-(p-tolyl)propyl 4- nitrobenzoate 3b - (1R*,3R*)-1-(4-(tert-butyl)phenyl)-2,2-dichloro-3-hydroxy-3-(4- nitrophenyl)propyl 4-nitrobenzoate 6a - ((2R*,3R*)-2-chloro-3-(4-nitrophenyl)oxiran-2-yl)(1-methyl-1H-pyrrol-2- yl)methanone 6f - (2R*,3R*)-2-chloro-3-(4-nitrophenyl)oxiran-2-yl)(p-tolyl)methanone 6h - ((2R*,3R*)-2-chloro-3-(4-nitrophenyl)oxiran-2-yl)(phenyl)methanone 1 H and 13 C NMR Spectra: 2b - 2,2-dichloro-1-(p-tolyl) ethanone 2b-d - 2,2-dichloro-2-deuterium-1-(p-tolyl) ethanone 2c - 1-(4-(tert-butyl)phenyl)-2,2-dichloroethan-1-one 2c-d - 1-(4-(tert-butyl)phenyl)-2,2-dichloroethan-1-one-2-d 2d - 2,2-dichloro-1-(5-methylfuran-2-yl)ethan-1-one 2d-d - 2,2-dichloro-1-(5-methylfuran-2-yl)ethan-1-one-2-d 2e - 2,2-dichloro-1-(1H-indol-3-yl)ethan-1-one 2f - 2,2-dichloro-1-(1-methyl-1H-indol-3-yl)ethan-1-one 2f-d - 2,2-dichloro-1-(1-methyl-1H-indol-3-yl)ethan-1-one-2-d S3 S3 S4 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15 S16 S17 S18 S19 S21 S23 S25 S27 S29 S31 S33 S35 S1

2 2h - 2,2-dichloro-3-hydroxy-3-(perfluorophenyl)-1-(p-tolyl)propan-1-one 2i - 2,2-dichloro-3-hydroxy-1-(5-methylfuran-2-yl)-3-(perfluorophenyl)propan-1- one 2j - 2,2-dichloro-3-hydroxy-1-(1H-indol-3-yl)-3-(perfluorophenyl)propan-1-one 2k - 2,2-dichloro-3-hydroxy-1-(1-methyl-1H-indol-3-yl)-3- (perfluorophenyl)propan-1-one 2m - 2,2-dichloro-3-hydroxy-3-(5-methylfuran-2-yl)-1-(p-tolyl) propan-1-one 2o - 2,2-dichloro-3-hydroxy-3-(4-nitrophenyl)-1-(p-tolyl)propan-1-one 2p - 1-(4-(tert-butyl)phenyl)-2,2-dichloro-3-hydroxy-3-(4-nitrophenyl)propan-1- one 2q - 2,2-dichloro-3-hydroxy-1-(1-methyl-1H-indol-3-yl)-3-(4- nitrophenyl)propan-1-one 2s - diethyl 2-(1,1-dichloro-2-oxo-2-(p-tolyl)ethyl)-2-hydroxymalonate 2t - diethyl 2-(1,1-dichloro-2-(1-methyl-1H-indol-3-yl)-2-oxoethyl)-2- hydroxymalonate 2v - 2,2-dichloro-1-(4-nitrophenyl)-3-(p-tolyl)propane-1,3-dione 2w - 1-(4-(tert-butyl)phenyl)-2,2-dichloro-3-(4-nitrophenyl)propane-1,3-dione 2x - 2,2-dichloro-1-(5-methylfuran-2-yl)-3-(4-nitrophenyl)propane-1,3-dione 2y - 2,2-dichloro-1-(1-methyl-1H-indol-3-yl)-3-(4-nitrophenyl)propane-1,3-dione 3a - (1R*,3R*)-2,2-dichloro-3-hydroxy-3-(4-nitrophenyl)-1-(p-tolyl)propyl 4- nitrobenzoate 3b - (1R*,3R*)-1-(4-(tert-butyl)phenyl)-2,2-dichloro-3-hydroxy-3-(4- nitrophenyl)propyl 4-nitrobenzoate 3c/4c - (1R*,3R*)-2,2-dichloro-3-hydroxy-3-(4-methoxyphenyl)-1-(ptolyl)propyl 4-methoxybenzoate and (1R*,3R*)-2,2-dichloro-3-hydroxy-1-(4- methoxyphenyl)-3-(p-tolyl)propyl 4-methoxybenzoate 3d/4d - (1R*,3R*)-3-(4-bromophenyl)-2,2-dichloro-3-hydroxy-1-(p-tolyl)propyl 4-bromobenzoate and (1R*,3R*)-1-(4-bromophenyl)-2,2-dichloro-3-hydroxy-3-(ptolyl)propyl 4-bromobenzoate 5a - (1R*,3R*)-1-(4-bromophenyl)-2,2-dichloro-3-(p-tolyl)propane-1,3-diol 6a - ((2R*,3R*)-2-chloro-3-(4-nitrophenyl)oxiran-2-yl)(1-methyl-1H-pyrrol-2- yl)methanone 6b ((2R*,3R*)-2-chloro-3-phenyloxiran-2-yl)(1-methyl-1H-pyrrol-2- yl)methanone 6c ((2R*,3R*)-3-(4-bromophenyl)-2-chlorooxiran-2-yl)(1-methyl-1H-pyrrol-2- yl)methanone 6d - ((2R*,3R*)-2-chloro-3-(4-iodophenyl)oxiran-2-yl)(1-methyl-1H-pyrrol-2- yl)methanone 6e - ((2R*,3R*)-2-chloro-3-(4-methoxyphenyl)oxiran-2-yl)(1-methyl-1H-pyrrol- 2-yl)methanone 6f - (2R*,3R*)-2-chloro-3-(4-nitrophenyl)oxiran-2-yl)(p-tolyl)methanone 6g - (4-(tert-butyl)phenyl)((2R*,3R*)-2-chloro-3-(4-nitrophenyl)oxiran-2- yl)methanone 6h - ((2R*,3R*)-2-chloro-3-(4-nitrophenyl)oxiran-2-yl)(phenyl)methanone 7a - 3-chloro-1-(1-methyl-1H-pyrrol-2-yl)-3-(4-nitrophenyl)propane-1,2-dione 7b - 3-chloro-3-(4-nitrophenyl)-1-(p-tolyl)propane-1,2-dione S37 S39 S41 S43 S45 S47 S49 S51 S53 S55 S57 S59 S61 S63 S65 S67 S69 S771 S73 S75 S77 S79 S81 S83 S85 S87 S89 S91 S93 S2

3 General experimental information 1 H and 13 C NMR spectra were recorded directly with a Jeol Lambda 500 MHz, Jeol ECS-400 MHz or Bruker Avance 300 MHz. HRMS data were provided by the EPSRC National Mass Spectrometry Service (University of Swansea). X-ray diffraction data was obtained on an Oxford Diffraction Gemini except for compound 6f which was collected on a Bruker D8 Venture. IR spectra were obtained as neat samples using a Varian 800 FT-IR Scimitar Series spectrometer scanning from cm -1.THF and Et 2 O were distilled from sodium/benzophenone and used directly. DCM was distilled from calcium hydride and used directly. 1d - 2,2,2-trichloro-1-(5-methylfuran-2-yl)ethan-1-one To a round bottom flask was added sequentially DCM (60 ml), 2,2,2-trichloroacetylchloride (3.7 ml, 33 mmol) and 2-methylfuran (2.463 g, 30 mmol). The solution was stirred for 24 hours under a nitrogen atmosphere. The solution was quenched with an aqueous solution of K 2 CO 3 (1.38 g in 50 ml of water) and separated. The organic layer was washed with 3x100 ml of water, 100 ml of brine and then dried using MgSO 4. The solvent was removed under reduced pressure to give a brown oil. The crude product was purified through silica gel column chromatography (petrol : ether = 4 : 1) to give 2,2,2-trichloro-1-(5-methylfuran-2- yl)ethan-1-one (1d) as a brown oil (4.43 g, 65%). R f : 0.50 (UV active, petrol 40/60 : ether = 4: 1). 1 H NMR (400 MHz, CDCl 3 ): δ H 7.57 (dd, J = 3.6, 0.8 Hz, 1H), 6.29 (dd, J = 3.6, 0.8 Hz, 1H), 2.47 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ C 170.0, 160.7, 143.5, 125.9, 109.7, 94.4, IR (neat): υ max /cm , 1500, 1211, 1031, 811, 742, 666. HRMS (pnsi): calcd for C 7 H 6 O 2 Cl 3 [M+H] + : , found S3

4 1e - 2,2,2-trichloro-1-(1H-indol-3-yl)ethan-1-one To a round bottom flask cooled to 0 o C was added sequentially DCM (40 ml), indole (1.17 g, 10 mmol) and pyridine (1.2 ml, 11 mmol). 2,2,2-trichloroacetylchloride (1.96 g, 11 mmol) was added into the solution for over 15 min. The solution was kept in fridge (5 o C) for 7 days during which time a precipitate had formed. The precipitate was filtered, washed with 50 ml methanol and 50 ml water respectively. The solid was dried under vacuum to give 2,2,2- trichloro-1-(1h-indol-3-yl)ethan-1-one (1e) as a light brown solid (2.28 g, 87%). Mp = o C. R f : 0.35 (UV active, petrol 40/60 : EtOAc = 7: 3). 1 H NMR (400 MHz, d6- DMSO): δ H (s, 1H), 8.60 (s, 1H), (m, 1H), (m, 1H), (m, 2H). 13 C NMR (100 MHz, d6-dmso): δ C 176.7, 136.7, 136.1, 127.1, 123.8, 123.1, 121.2, 112.9, 104.7, IR (neat): υ max /cm , 2981, HRMS (pnsi): calcd for C 10 H 7 NOCl 3 [M+H] + : , found EA calcd for C 10 H 6 Cl 3 NO: C, 45.75; H, 2.30; N, found: C, 45.82; H, 2.30; N, f - 2,2,2-trichloro-1-(1-methyl-1H-indol-3-yl)ethan-1-one To a round bottom flask under cooled to 0 o C was added sequentially DCM (20 ml), 1- methyl-1h-indole (0.655 g, 5 mmol) and pyridine (0.4 ml, 5.1 mmol). 2,2,2- trichloroacetylchloride (0.899 g, 5.1 mmol) was added to the solution over 15 min. The solution was kept in fridge (5 o C) for 3 days during which time a precipitate had formed. The precipitate was filtered then dissolved in DCM (25 ml). The solution was washed with 5x50 ml HCl 1M, dried over MgSO 4 and the organic solvent removed under reduced pressure to give 2,2,2-trichloro-1-(1-methyl-1H-indol-3-yl)ethan-1-one (1f) without further purification as a colourless solid (1.03 g, 75%). Mp = o C. R f : 0.52 (UV active, petrol 40/60 : ether = 7: 3). 1 H NMR (400 MHz, CDCl 3 ): δ H 8.44 (s, 1H), (m, 1H), (m, 1H), (m, 2H), 3.89 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ C 176.7, 138.0, 136.8, 133.9, 128.2, 124.0, 123.6, 122.6, 110.0, 105.3, IR (neat): υ max /cm , HRMS (pnsi): calcd for C 11 H 9 NOCl 3 [M+H] + : , found EA calcd for C 11 H 8 Cl 3 NO: C, 47.78; H, 2.92; N, found: C, 47.88; H, 2.85; N, S4

5 1e - 2,2,2-trichloro-1-(1H-indol-3-yl)ethan-1-one Table 1 Crystal data and structure refinement for mjh85. Identification code mjh85 Empirical formula C 10 H 6 Cl 3 NO Formula weight Temperature/K 150 Crystal system orthorhombic Space group Pnma a/å (14) b/å (4) c/å (5) α/ 90 β/ 90 γ/ 90 Volume/Å (12) Z 4 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -27 h 26, -6 k 9, -9 l 7 Reflections collected 5188 Independent reflections 1240 [R int = , R sigma = ] Data/restraints/parameters 1240/0/91 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.24 S5

6 1f - 2,2,2-trichloro-1-(1-methyl-1H-indol-3-yl)ethan-1-one Table 1 Crystal data and structure refinement for mjh88. Identification code mjh88 Empirical formula C 11 H 8 NOCl 3 Formula weight Temperature/K Crystal system monoclinic Space group P2 1 /c a/å (5) b/å (4) c/å (5) α/ 90 β/ (5) γ/ 90 Volume/Å (9) Z 4 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -12 h 13, -15 k 15, -14 l 13 Reflections collected 9535 Independent reflections 2573 [R int = , R sigma = ] Data/restraints/parameters 2573/0/146 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.24 S6

7 2a - 2,2-dichloro-1-(1-methyl-1H-pyrrol-2-yl)ethan-1-one Table 1 Crystal data and structure refinement for mjh91. Identification code mjh91 Empirical formula C 7 H 7 NOCl 2 Formula weight Temperature/K 150 Crystal system orthorhombic Space group P a/å (3) b/å (4) c/å (6) α/ 90 β/ 90 γ/ 90 Volume/Å (7) Z 4 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -7 h 7, -14 k 13, -18 l 16 Reflections collected 6723 Independent reflections 1892 [R int = , R sigma = ] Data/restraints/parameters 1892/0/101 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.34 Flack parameter 0.02(2) S7

8 2f - 2,2-dichloro-1-(1-methyl-1H-indol-3-yl)ethan-1-one Table 1 Crystal data and structure refinement for mjh92. Identification code mjh92 Empirical formula C 11 H 9 Cl 2 NO Formula weight Temperature/K 150 Crystal system monoclinic Space group P2 1 /c a/å (4) b/å (6) c/å (11) α/ 90 β/ (5) γ/ 90 Volume/Å (12) Z 4 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -9 h 9, -14 k 14, -19 l 8 Reflections collected 4305 Independent reflections 4305 [R int =?, R sigma = ] Data/restraints/parameters 4305/0/138 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.38 S8

9 2h - 2,2-dichloro-3-hydroxy-3-(perfluorophenyl)-1-(p-tolyl)propan-1-one Table 1 Crystal data and structure refinement for mjh82. Identification code mjh82 Empirical formula C 16 H 9 O 2 F 5 Cl 2 Formula weight Temperature/K 150 Crystal system orthorhombic Space group Pccn a/å (5) b/å (9) c/å (8) α/ 90 β/ 90 γ/ 90 Volume/Å (4) Z 16 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -14 h 18, -22 k 27, -27 l 26 Reflections collected Independent reflections 7084 [R int = , R sigma = ] Data/restraints/parameters 7084/396/461 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.27 S9

10 2j - 2,2-dichloro-3-hydroxy-1-(1H-indol-3-yl)-3-(perfluorophenyl)propan-1-one Table 1 Crystal data and structure refinement for mjh90. Identification code mjh90 Empirical formula C 17 H 8 NO 2 F 5 Cl 2 Formula weight Temperature/K Crystal system triclinic Space group P-1 a/å (3) b/å (6) c/å (7) α/ (5) β/ (4) γ/ (4) Volume/Å (8) Z 2 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -9 h 8, -10 k 12, -15 l 15 Reflections collected 6097 Independent reflections 3273 [R int = , R sigma = ] Data/restraints/parameters 3273/1/252 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.36 S10

11 2k - 2,2-dichloro-3-hydroxy-1-(1-methyl-1H-indol-3-yl)-3-(perfluorophenyl)propan-1- one Table 1 Crystal data and structure refinement for mjh94. Identification code mjh94 Empirical formula C 18 H 10 NO 2 F 5 Cl 2 Formula weight Temperature/K Crystal system triclinic Space group P-1 a/å (6) b/å (7) c/å (10) α/ (7) β/ (6) γ/ (7) Volume/Å (12) Z 2 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -8 h 10, -10 k 12, -14 l 15 Reflections collected 7559 Independent reflections 3605 [R int = , R sigma = ] Data/restraints/parameters 3605/0/255 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.30 S11

12 2o - 2,2-dichloro-3-hydroxy-3-(4-nitrophenyl)-1-(p-tolyl)propan-1-one Table 1 Crystal data and structure refinement for mjh86. Identification code mjh86 Empirical formula C 16 H 13 NO 4 Cl 2 Formula weight Temperature/K 150 Crystal system triclinic Space group P-1 a/å (5) b/å (6) c/å (5) α/ (4) β/ (4) γ/ (5) Volume/Å (8) Z 2 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -11 h 10, -13 k 12, -12 l 12 Reflections collected Independent reflections 3394 [R int = , R sigma = ] Data/restraints/parameters 3394/0/212 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.29 S12

13 2t - diethyl 2-(1,1-dichloro-2-(1-methyl-1H-indol-3-yl)-2-oxoethyl)-2-hydroxymalonate Table 1 Crystal data and structure refinement for mjh95. Identification code mjh95 Empirical formula C 18 H 19 NO 6 Cl 2 Formula weight Temperature/K Crystal system triclinic Space group P-1 a/å (5) b/å (6) c/å (7) α/ (5) β/ (6) γ/ (5) Volume/Å (10) Z 2 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -9 h 10, -12 k 9, -13 l 14 Reflections collected 7004 Independent reflections 3683 [R int = , R sigma = ] Data/restraints/parameters 3683/0/251 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.31 S13

14 3a - (1R*,3R*)-2,2-dichloro-3-hydroxy-3-(4-nitrophenyl)-1-(p-tolyl)propyl 4- nitrobenzoate Table 1 Crystal data and structure refinement for mjh87. Identification code mjh87 Empirical formula C 23 H 18 N 2 O 7 Cl 2 Formula weight Temperature/K 150 Crystal system orthorhombic Space group P a/å (4) b/å (7) c/å (8) α/ 90 β/ 90 γ/ 90 Volume/Å (18) Z 4 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ 5.79 to Index ranges -8 h 11, -18 k 20, -20 l 21 Reflections collected Independent reflections 4711 [R int = , R sigma = ] Data/restraints/parameters 4711/0/309 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.21 Flack parameter 0.03(4) S14

15 3b - (1R*,3R*)-1-(4-(tert-butyl)phenyl)-2,2-dichloro-3-hydroxy-3-(4-nitrophenyl)propyl 4-nitrobenzoate Table 1 Crystal data and structure refinement for mjh83. Identification code mjh83 Empirical formula C 27 H 24 N 2 O 7 Cl 5 Formula weight Temperature/K Crystal system monoclinic Space group Pn a/å (3) b/å (6) c/å (6) α/ 90 β/ (4) γ/ 90 Volume/Å (11) Z 2 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -8 h 8, -18 k 15, -19 l 20 Reflections collected 9761 Independent reflections 4882 [R int = , R sigma = ] Data/restraints/parameters 4882/311/370 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.46 Flack parameter -0.01(2) S15

16 6a - ((2R*,3R*)-2-chloro-3-(4-nitrophenyl)oxiran-2-yl)(1-methyl-1H-pyrrol-2- yl)methanone Table 1 Crystal data and structure refinement for mjh Identification code mjh Empirical formula C 14 H 11 O 4 ClN 2 Formula weight Temperature/K Crystal system monoclinic Space group P2 1 /n a/å (4) b/å (8) c/å (4) α/ 90 β/ (6) γ/ 90 Volume/Å (12) Z 4 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -11 h 10, -25 k 28, -11 l 11 Reflections collected Independent reflections 3057 [R int = , R sigma = ] Data/restraints/parameters 3057/21/220 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.34 S16

17 6f - (2R*,3R*)-2-chloro-3-(4-nitrophenyl)oxiran-2-yl)(p-tolyl)methanone Table 1 Crystal data and structure refinement for mjh Identification code mjh Empirical formula C 16 H 12 NO 4 Cl Formula weight Temperature/K Crystal system monoclinic Space group Cc a/å (2) b/å (10) c/å (2) α/ 90 β/ (4) γ/ 90 Volume/Å (4) Z 4 ρ calc mg/mm m/mm F(000) Crystal size/mm Radiation Mo Kα (λ = ) 2Θ range for data collection to Index ranges -20 h 20, -9 k 9, -18 l 18 Reflections collected 9693 Independent reflections 3415[R(int) = ] Data/restraints/parameters 3415/2/200 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.20 Flack parameter 0.00(6) S17

18 6h - ((2R*,3R*)-2-chloro-3-(4-nitrophenyl)oxiran-2-yl)(phenyl)methanone Table 1 Crystal data and structure refinement for mjh140034_fa. Identification code mjh140034_fa Empirical formula C 15 H 10 NO 4 Cl Formula weight Temperature/K (10) Crystal system monoclinic Space group P2 1 /n a/å (9) b/å (16) c/å (16) α/ 90 β/ (10) γ/ 90 Volume/Å (3) Z 4 ρ calc g/cm µ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -9 h 9, -15 k 15, -19 l 19 Reflections collected Independent reflections 3041 [R int = , R sigma = ] Data/restraints/parameters 3041/0/190 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole / e Å /-0.28 S18

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