Organocatalytic Synthesis of cis-2,3-aziridine Aldehydes by a Postreaction Isomerization. Supporting Information

Transcription

1 Organocatalytic Synthesis of cis-2,3-aziridine Aldehydes by a Postreaction Isomerization Supporting Information Sebastian Frankowski, Jan Bojanowski, Maciej Saktura, Marta Romaniszyn, Piotr Drelich and Łukasz Albrecht* Institute of Organic Chemistry, Department of Chemistry Lodz University of Technology Zeromskiego 6, Łódź, Poland lukasz.albrecht@p.lodz.pl Table of contents. General methods S2 2. Organocatalytic cis-aziridination of α,β-unsaturated aldehydes 2 general procedure S3 3. Organocatalytic syn-aminohydroxylation of α,β-unsaturated aldehydes 2 general S8 procedure 4. Organocatalytic cis-aziridination of α,β-unsaturated aldehydes 2 mechanistic S experiments 5. Assignment of the absolute configuration S5 6. NMR data S6 7. HPLC traces S43 S

2 . General methods NMR spectra were acquired on a Bruker Ultra Shield 700 instrument, running at 700 MHz for H and 76 MHz for 3 C, respectively. Chemical shifts (δ) are reported in ppm relative to residual solvent signals (CDCl 3: 7.26 ppm for H NMR, 77.6 ppm for 3 C NMR). Mass spectra were recorded on a Bruker Maxis Impact spectrometer using electrospray (ES+) ionization (referenced to the mass of the charged species). Optical rotations were measured on a Perkin-Elmer 24 polarimeter and [ ] D values are given in deg cm g - dm - ; concentration c is listed in g (00 ml) -. Analytical thin layer chromatography (TLC) was performed using pre-coated aluminum-backed plates (Merck Kieselgel 60 F254) and visualized by ultraviolet irradiation or KMnO 4 or phosphamolybdic acid stain. The enantiomeric ratio (er) of the products was determined by chiral stationary phase HPLC (Daicel Chiralpak IA and ID). Unless otherwise noted, analytical grade solvents and commercially available reagents were used without further purification. For flash chromatography (FC) silica gel (Silica gel 60, mesh, Fluka). α,β- Unsaturated aldehydes 2g and 2h 2 and aziridinating reagents 3a 3 and 3c 4 were prepared according to literature procedures. Avi, M.; Gaisberger, R.; Feichtenhofer, S.; Griengl, H. Tetrahedron 2009, 65, Albrecht, Ł.; Dickmeiss, G.; Cruz Acosta, F.; Rodríguez-Escrich, C.; Davis, R. L.; Jørgensen, K. A. J. Am. Chem. Soc. 202, 34, Drelich, P.; Skrzyńska, A.; Albrecht, Ł. Eur. J. Org. Chem. 206, 25, Albrecht, Ł.; Jiang, H.; Dickmeiss, G.; Gschwend, B.; Hansen, S. G.; Jørgensen, K. A. J. Am. Chem. Soc. 200, 32, 988. S2

3 2. Organocatalytic cis-aziridination of α,β-unsaturated aldehydes 2 general procedure In an ordinary 4 ml glass vial, equipped with a Teflon-coated magnetic stirring bar and a screw cap, catalyst 5b (0.2 equiv, 0.02 mmol, 6.5 mg), sodium acetate (.5 equiv, 0.5 mmol, 2.3 mg), NsNHOTs 3a ( equiv, 0. mmol, 37.2 mg) and the corresponding aldehyde 2 (.5 equiv, 0.5 mmol) were dissolved in CH 2Cl 2 (0.8 ml) and stirring was maintained for 6-6 h at ambient temperature. Pure product cis- was isolated by flash chromatography on silica gel (eluent: CH 2Cl 2). Aldehydes cis- proved unstable and should not be stored for longer times. In the present work they were subjected to the reduction according to the following procedure. Reduction of cis-2,3-aziridine aldehyde cis- to the corresponding alcohol general procedure In an ordinary 4 ml glass vial, equipped with a Teflon-coated magnetic stirring bar and a screw cap, corresponding aziridine cis- ( equiv, 0.05 mmol) was dissolved in a glacial acetic acid (0,4 ml) and the resulting solution was cooled in cold water bath. Subsequently, sodium borohydride (5 equiv, 9.5 mg) was added, and reaction was stirred for 30 min at room temperature. Reaction was quenched with water (5 ml), extracted with dichloromethane (3 x 0 ml). Combined organic layers were washed with saturated aqueous solution of sodium bicarbonate ( x 5 ml) and water ( x 5 ml), dried over anhydrous MgSO 4, filtered and concentrated in vacuo. Pure product was isolated by flash chromatography on silica gel (eluent: hexane:acetone 80:20). cis-a (2R,3R)-3-Hexyl--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry ) Following the general procedure (reaction time 6 h, 9: dr), pure diastereomer cis-a was isolated by FC on silica gel (eluent: CH 2Cl 2) as a pale yellow viscous oil (28 mg, 82% yield,). H NMR (700 MHz, CDCl 3) δ: 9.43 (d, J = 4.4 Hz, H), (m, H), (m, 3H), 3.60 (dd, J = 7.6, 4.4 Hz, H), (m, H), (m, H), (m, H),.5.44 (m, H), (m, H), (m, 2H),.29.2 (m, 5H), 0.87 (t, J = 7. Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 94.9, 48.7, 35.0, 32.6, 3.9, 3.6, 24.8, 49., 47.5, 3.6, 28.7, , 27., 22.6, 4.. [α] D = +5.2 (c =.0, CHCl 3). In order to determine the er, the product was converted to the alcohol a. Procedure for the mmol scale preparation of cis-a (2R,3R)-3-hexyl--((2-nitrobenzene-- sulfonyl)aziridine-2-carbaldehyde In a 25 ml roundbottom flask equipped with a Teflon-coated magnetic stirring bar and a glass stopper, catalyst 5b (0.2 equiv., 0.2 mmol, 65. mg), sodium acetate (.5 equiv.,.5 mmol, 23 mg), NsNHOTs 3a ( equiv.,.0 mmol, mg) and the trans-2-nonenal (.5 equiv.,.5 mmol, 20.3 mg) were dissolved in CH 2Cl 2 (8 ml) and stirring was maintained for 6h at ambient temperature (9: dr). Pure product cis- was isolated by flash chromatography on silica gel (eluent: CH 2Cl 2) as a pale yellow viscous oil (77 mg, 52% yield,). In order to determine the er, the product was converted to the alcohol a. S3

4 The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 26.6 min., τ minor = 23.7 min. (93:7 er) a ((2R,3R)-3-Hexyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR (700 MHz, CDCl 3) δ: 8.20 (m, H), (m, 3H), (m, H), (m, H), (m, H), (m, H),.80 (bs, H), (m, 2H), (m, 2H),.33.8 (m, 6H), 0.86 (t, J = 7. Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 48.7, 34.6, 32.3, 32., 3.3, 24.4, 59.5, 47., 3.7, 28.9, 27.3, 27., 22.6, 4.2. HRMS calculated for [C 5H 22N 2O 5S+H + ]: ; found: [α] D 2 = -8.0 (c =.0, CHCl 3). The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 26.6 min., τ minor = 23.7 min. (94:6 er). cis-b (2R,3R)--((2-Nitrobenzene--sulfonyl)-3-pentylaziridine-2-carbaldehyde (Table 2, entry 2) Following the general procedure (reaction time 6 h, 9: dr), pure diastereomer cis-b was isolated by FC on silica gel (eluent:ch 2Cl 2) as a pale yellow viscous oil (4 mg, 44% yield,). H NMR (700 MHz, CDCl 3) δ: 9.43 (d, J = 4.4 Hz, H), (m, H), (m, 3H), 3.60 (dd, J = 7.7, 4.4 Hz, H), 3.34 (td, J = 7.5, 6.5 Hz, H), (m, H), (m, H),.5.45 (m, H), (m, H).3.28 (m, 4H), 0.87 (t, J = 7. Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 94.9, 48.7, 35.0, 32.6, 3.9, 3.6, 24.8, 49.0, 47.5, 3.2, 28.0, 26.8, 22.5, 4.0. [α] D 27 = +8.3 (c = 0.5, CHCl 3). In order to determine the er, the product was converted to the alcohol b. b ((2R,3R)--(2-Nitrobenzene--sulfonyl)-3-pentylaziridin-2-yl)methanol H NMR (700 MHz, CDCl 3) δ: (m, H), (m, 3H), (m, H), (m, H), 3.27 (ddd, J = 7.3, 6.7, 4.9 Hz, H), 3.4 (td, J = 7.5, 6.2 Hz, H),.79 (bs, H), (m, 2H),.4.35 (m, 2H), (m, 4H), (m, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 48.7, 34.6, 32.3, 32., 3.3, 24.4, 59.6, 47., 3.4, 29.8, 27., 27.0, 22.5, 4.0. HRMS calculated for [C 4H 20N 2O 5S+H + ]: ; found: [α] D 2 = -7.3 (c = 0.47, CHCl 3). The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 28.4 min., τ minor = 26.2 min. (9.5:8.5 er). cis-c (2R,3R)-3-Butyl--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 3) Following the general procedure (reaction time 6 h, 9: dr), pure diastereomer cis- a was isolated by FC on silica gel (eluent: CH 2Cl 2) as a pale yellow viscous oil (22 mg, 70% yield,). H NMR (700 MHz, CDCl 3) δ: 9.43 (d, J = 4.4 Hz, H), (m, H), (m, 3H), 3.60 (dd, J = 7.7, 4.5 Hz, H), (m, H), (m, H), (m, H), (m, H),.42.3 (m, 3H), 0.88 (t, J = 7.2 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 94.9, 48.7, , 32.6, 3.9, 3.6, 24.8, 49.0, 47.5, 29., 27.7, 22., 3.9. [α] D =.9 (c =.0, CHCl 3). In order to determine the er, the product was converted to the alcohol c. S4

5 c ((2R,3R)-3-Butyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR (700 MHz, CDCl 3) δ: (m, H), (m, 3H), (m, H), (m, H), (m, H), (m, H), (m, H), (m, H), (m, H), (m, 4H), 0.87 (t, J = 7. Hz, 4H). 3 C NMR (76 MHz, CDCl 3) δ: 48.7, 34.6, 32.3, 32., 3.3, 24.4, 59.5, 47., 47.0, 29.4, 26.8, 22.3, 4.0. HRMS calculated for [C 3H 8N 2O 5S+H + ]: ; found: [α] D 2 = -3.7 (c =.0, CHCl 3). The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 3.9 min., τ minor = 29.8 min. (9:9 er). cis-d (2R,3R)--((2-Nitrobenzene--sulfonyl)-3-propylaziridine-2-carbaldehyde (Table 2, entry 4) Following the general procedure (reaction time 6 h, 0: dr), pure diastereomer cis- d was isolated by FC on silica gel (eluent:ch 2Cl 2) as a pale yellow viscous oil (0 mg, 34% yield). H NMR (700 MHz, CDCl 3) δ: 9.43 (d, J = 4.4 Hz, H), (m, H), (m, 3H), 3.6 (dd, J = 7.7, 4.4 Hz, H), 3.35 (td, J = 7.5, 6.2 Hz, H), (m, H), (m, H), (m, 2H), 0.96 (t, J = 7.4 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 94.2, 48.7, 35., 32.7, , 3.6, 24.8, 49., 47.3, 30.0, 20.5, 3.6. [α] D = +3.0 (c =.0, CHCl 3). In order to determine the er, the product was converted to the alcohol d. d ((2R,3R)--((2-Nitrobenzene--sulfonyl)-3-propylaziridin-2-yl)methanol H NMR (700 MHz, CDCl 3) δ: 8.20 (dd, J = 7.4,.3Hz, H), (m, 3H), (m, H), (m, H), 3.26 (ddd, J = 7.4, 6.7, 4.9 Hz, H), 3.6 (td, J = 7.5, 6. Hz, H),.80 (t, J = 6.3 Hz, H),.65.5 (m, 2H), (m, 2H), 0.93 (t, J = 7.4 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 48.8, 34.6, 32.3, 32., 3.3, 24.5, 59.5, 47., 46.8, 29.2, 20.7, 3.8. HRMS calculated for [C 2H 6N 2O 5S+H + ]: ; found: [α] D 9 = -8. (c =.0, CHCl 3). The er was determined by HPLC using a chiral Chiralpack IA column [hexane:i-proh, 95:5]; column temperature 30 C; flow rate.0 ml/min; τ major = 67.8 min., τ minor = 62.9 min. (90:0 er). cis-e (2S,3S)-3-Ethyl--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 5) Following the modified general procedure (reaction performed using ent-5b as catalyst, reaction time 6 h, 4: dr), pure diastereomer cis-e was isolated by FC on silica gel (eluent: CH 2Cl 2) as a pale yellow viscous oil (8 mg, 62% yield). H NMR (700 MHz, CDCl 3) δ: 9.43 (d, J = 4.4 Hz, H), (m, H), (m, 3H), 3.6 (dd, J = 7.6, 4.4 Hz, H), 3.3 (td, J = 7.5, 6.3 Hz, H), (m, H), (m, H),.05 (t, J = 7.4 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) 20 δ: 94.9, 48.7, 35., 32.7, 3.9, 3.6, 24.8, 49.2, 48.7, 2.6,.4. [α] D = -4.2 (c =.0, CHCl 3). In order to determine the er, the product was converted to the alcohol e. e ((2S,3S)-3-Ethyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR (700 MHz, CDCl 3) δ: 8.20 (d, J = 7.6 Hz, H), (m, 3H), (m, H), (m, H), 3.27 (td, J = 6.9, 5.0 Hz, H), 3. (q, J = 7. Hz, H),.84 (t, J = 5.8 Hz, H), (m, 2H), 0.99 (t, J = 7.5 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 48.7, 34.6, 32.3, 32.0, 3.3, 24.4, 59.5, 48.2, 47.2, 20.6,.67. HRMS calculated for [C H 4N 2O 5S+H + ]: ; found: [α] D 2 =.4 (c =.0, CHCl 3). The er was determined S5

6 by HPLC using a chiral Chiralpack IA column [hexane:i-proh, 90:0]; column temperature 30 C; flow rate.0 ml/min; τ major = 27.7 min., τ minor = 3.2 min. (0:90 er). cis-f (2R,3R)-3-Methyl--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 6) Following the general procedure (reaction time 6 h, 7:3 dr), pure diastereomer cis- f was isolated by FC on silica gel (eluent:ch 2Cl 2) as a pale yellow viscous oil (3 mg, 48% yield). H NMR (700 MHz, CDCl 3) δ: 9.44 (d, J = 4.4 Hz, H), (m, H), (m, 3H), 3.6 (dd, J = 7.7, 4.3 Hz, H), 3.45 (dq, J = 7.7, 5.9 Hz, H),.48 (d, J = 5.9 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) 20 δ: 95.0, 48.7, 35.0, 32.8, 32.2, 3.7, 24.9, 48.4, 43.8, 3.4. [α] D = 53.5 (c =.0, CHCl 3). In order to determine the er, the product was converted to the alcohol f. f ((2R,3R)-3-Methyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR (700 MHz, CDCl 3) δ: (m, H), (m, 3H), 3.83 (dd, J =.7, 3.7 Hz, H), (m, H), (m, 2H),.86 (s, H), (m, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 48.7, 34.6, 32.5, 32.4, 3.3, 24.5, 59.4, 46.6, 43.0, 2.4. HRMS calculated for [C 0H 2N 2O 5S+H + ]: ; found: [α] D 23 = 30.9 (c =.0, CHCl 3). The er was determined by HPLC using a chiral Chiralpack IA column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 40.7 min., τ minor = 32.4 min. (75.5:24.5 er). cis-g (2R,3R)-3-Benzyl--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 7) Following the general procedure (reaction time 6 h, 9: dr), pure diastereomer cis- g was isolated by FC on silica gel (eluent:ch 2Cl 2) as a pale yellow viscous oil (20 mg, 58% yield). H NMR (700 MHz, CDCl 3) δ: 9.50 (d, J = 4. Hz, H), 8.5 (dd, J = 7.7,.3 Hz, H), (m, 2H), (m, H), (m, 3H), (m, 2H), 3.67 (dd, J = 7.6, 4. Hz, H), 3.58 (q, J = 7.0 Hz, H), 3.7 (dd, J = 4.8, 6.5 Hz, H), 2.9 (dd, J = 4.7, 7.0 Hz, H). 3 C NMR (76 MHz, CDCl 3) δ: 94.5, 48.7, 36.0, 35., 32.6, 3.6, 3.5, 29.0 (2C), 28.9 (2C), 27.4, 24.8, 48.4, , [α] D = 25.8 (c =.0, CHCl 3). In order to determine the er, the product was converted to the alcohol g. g ((2R,3R)-3-Benzyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR (700 MHz, CDCl 3) δ: 8.02 (dd, J = 7.9,.3 Hz, H), (m, 2H), 7.65 (td, J = 7.6,.5 Hz, H), (m, 5H), 3.95 (dd, J = 2.5, 4.9 Hz, H), 3.89 (dd, J = 2.3, 6. Hz, H), 3.38 (q, J = 7.0 Hz, H), (m, H), 3.04 (dd, J = 4.6, 7.0 Hz, H), 2.86 (dd, J = 4.6, 6.8 Hz, H),.89 (s, H). 3 C NMR (76 MHz, CDCl 3) δ: 48.7, 37., 34.6, 32.3, 3.8, 3.2, 28.8 (2C), 28.8 (2C), 27.0, 24.5, 59.4, 47.9, 46.2, HRMS calculated for [C 6H 6N 2O 5S+H + ]: ; found: [α] D 2 = -.0 (c =.0, CHCl 3). The er was determined by HPLC using a chiral Chiralpack IA column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 4.8 min, τ minor = 8.7 min, (94:6 er). [α] D 2 = -.0 (c =.0, CHCl 3). S6

7 cis-h (2R,3S)-3-((Benzyloxy)methyl)--((2-nitrobenzene--sulfonyl)aziridine- 2-carbaldehyde (Table 2, entry 8) Following the general procedure (reaction time 6 h, 9: dr), mixture of diastereomers trans and cis-h was isolated by FC on silica gel (eluent: CH 2Cl 2) as a pale yellow viscous oil (28 mg, 77% yield). H NMR (700 MHz, CDCl 3) δ: 9.38 (d, J = 4.0 Hz, H), (m, H), (m, 3H), (m, 3H), (m, 2H), 4.50 (s, 2H), 3.87 (dd, J =.6,4.0Hz, H), 3.83 (dd, J =.6, 3.8 Hz, H), 3.64 (dd, J = 7.7, 4.0 Hz, H), 3.59 (dt, J = 7.6, 3.8 Hz, H). 3 C NMR (76 MHz, CDCl 3) δ: 94., 48.6, 37.0, 35., 32.8, 3.9, 3.7, 28.6 (2C), 28.2, 27.9 (2C), 25.0, 73.6, 65.2, 47.7, 47.. [α] D 22 = +9.4 (c =.0, CHCl 3). In order to determine the er, the product was converted to the alcohol h. h ((2R,3S)-3-((Benzyloxy)methyl)--((2-nitrobenzene--sulfonyl)aziridin- 2-yl)methanol H NMR (700 MHz, CDCl 3) δ: (m, H), (m, 3H), (m, 5H), 4.57 (d, J =.7 Hz, H), 4.50 (d, J =.7 Hz, H), (m, 2H), (m, H); 3.57 (dd, J = 0.9, 6,8 Hz, H), 3.42 (dd, J = 3.3, 6.7, H), 3.36 (dd, J= 6.5, 2.9, H), (m, H) 3 C NMR (76 MHz, CDCl 3), δ: 48.6, 37.2, 34.7, 32.5, 32.0, 3.4, 28.7 (2C), 28.3, 28.0 (2C), 24.6, 73.6, 66.7, 59.7, 45.3, 44.. HRMS calculated for [C 7H 8N 2O 6S+H + ]: ; found: [α] D 23 = +5.3 (c =.0, CHCl 3). The er was determined by HPLC using a chiral Chiralpack IF column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 59.2 min., τ minor = 35.4 min. (89.5:0.5 er). cis-i (2R,3R)-3-((Z)-Hex-3-en--yl)--((2-nitrobenzene-- sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 9) Following the general procedure (reaction time 6 h, 6: dr), pure diastereomer cis-i was isolated by FC on silica gel (eluent: hexanes:acetone, 80:20) as a yellow viscous oil (8 mg, 54% yield). H NMR (700 MHz, CDCl 3) δ: 9.42 (d, J = 4.4 Hz, H), 8.26 (d, J = 7. Hz, H), (m, 3H), 5.42 (dtt, J = 0.3, 7.2,.4 Hz, H), 5.26 (dtt, J = 0.6, 7.3,.5 Hz, H), 3.60 (dd, J = 7.6, 4.3 Hz, H), 3.35 (q, J = 7. Hz, H), 2.20 (q, J = 7.4 Hz, 2H), (m, 2H),.88 (dq, J = 4.2, 7. Hz, H),.65 (dq, J = 4.5, 7.4 Hz, H), 0.95 (t, J = 7.5 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 94.6, 48.7, 35., 34., 32.7, 3.9, 3.6, 26., 24.8, 48.9, , 28., 24.6, 20.7, 4.3. [α] D = +9. (c =.0, CHCl 3). In order to determine the er, the product was converted to the alcohol i. i ((2R,3R)-3-((Z)-Hex-3-en--yl)--((2-nitrobenzene-- sulfonyl)aziridin-2-yl)methanol H NMR (700 MHz, CDCl 3) δ: 8.2 (dd, J = 7.6,.6 Hz, H), (m, 3H), 5.40 (dtt, J = 0.2, 7.2,.4 Hz, H), 5.29 (dtt, J = 0.7, 7.4,.6 Hz, H), (m, H), 3.75 (dd, J= 2.3, 6.5 Hz, H), 3.27 (ddd, J = 7.3, 6.5, 5.0 Hz, H), 3.6 (q, J = 7.0 Hz, H), 2.5 (q, J = 7.5 Hz, 2H), 2.00 (p, J = 7.4, 2H),.80 (bs, H),.74 (dq, J = 4.5, 7.2 Hz, H),.60 (dtd, J = 4., 7.7, 6.4 Hz, H), 0.94 (t, J = 7.5 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 48.7, 34.6, 33.5, 32.3, 32., 3.3, 27.0, 24.5, 59.5, 47.0, 46.76, 27.4, 24.9, 20.6, 4.4. HRMS calculated for [C 5H 20N 2O 5S+H + 5 ]: 34.66; found: [α] D = -4. (c =.0, CHCl 3). The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i-proh, 95:5]; column temperature 30 C; flow rate.0 ml/min; τ major = 29.6 min., τ minor = 23.3 min. (9:9 er). S7

8 3. Organocatalytic syn-aminohydroxylation of α,β-unsaturated aldehydes 2 general procedure In an ordinary 4 ml glass vial, equipped with a Teflon-coated magnetic stirring bar and a screw cap, catalyst 5b (0.2 equiv., 0.02 mmol, 6.5 mg), sodium acetate (.5 equiv., 0.5 mmol, 2.3 mg), NsNHOTs 3a ( equiv., 0. mmol, 37.2mg) and the corresponding aldehyde 2 (.5 equiv., 0.5 mmol) were dissolved in CH 2Cl 2 (0.8 ml) and stirring was maintained for 6-6h at ambient temperature. Next, methanolic solution of sodium methoxide (0.5 M, 2 equiv., 0.2 mmol, 0.4 ml) was added and the resulting mixture stirred for additional 6h at ambient temperature. Subsequently, the reaction was quenched with brine (5 ml) and the mixture was extracted with ethyl acetate (3x0 ml). Combined organic layers were washed with brine (0 ml) and dried over anhydrous MgSO 4, filtered and concentrated in vacuo. Crude product 9 was purified by flash chromatography on silica gel. 9a N-((2S,3R)-2-Hydroxy-,-dimethoxynonan-3-yl)-2-nitrobenzene-- sulfonamide (Table 3, entry ). Following the general procedure, pure diastereomer syn-9a was isolated by FC on silica gel (eluent: hexanes:acetone 80:20) as a pale yellow viscous oil (8 mg, 45% yield). H NMR (700 MHz, CDCl 3) δ: (m, H), (m, H), (m, 2H), 5.68 (d, J = 9.4 Hz, H), 4.30 (d, J = 7.5 Hz, H), (m, H), 3.5 (d, J = 7.3 Hz, H), 3.42 (s, 3H), 3.4 (s, H), 2.32 (bs, H), (m, H), (m, H),.20. (m, 6H),.0.04 (m, 2H), 0.82 (t, J = 7.3 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 47.9, 35.9, 33.3, 32.9, 30.5, 25.3, 04.5, 7.7, 56.3, 55.0 (2C), 33.0, 3.7, 29.0, 26.0, 22.6, 4.. HRMS calculated for [C 7H 28N 2O 7S+H + ]: ; found: [α] D = -6.7 (c =, CHCl 3). The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 25.7 min., τ minor = 2.0 min. (9.5:8:5 er). 9b N-((2S,3R)-2-Hydroxy-,-dimethoxyoctan-3-yl)-2-nitrobenzene-- sulfonamide (Table 3, entry 2) Following the general procedure, pure diastereomer syn-9b was isolated by FC on silica gel (eluent: hexanes:acetone 4:) as a pale yellow viscous oil (3 mg, 34% yield). H NMR (700 MHz, CDCl 3) δ: (m, H), (m, H), (m, 2H), 5.68 (d, J = 8.8 Hz, H), 4.30 (d, J = 7.5 Hz, H), (m, H), 3.5 (dd, J = 7.5,.6 Hz, H), 3.42 (s, 3H), 3.4 (s, 3H), 2.32 (bs, H) (m, H), (m, H),.8.0 (m, 6H), (m, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 47.9, 35.9, 33.3, 32.9, 30.5, 25.4, 04.5, 7.7, 56.3, S8

9 55.0 (2C), 33.0, 3.5, 25.7, 22.5, 4.0. HRMS calculated for [C 6H 26N 2O 7S+H + ]: ; found: [α] D 20 = (c = 0.57, CHCl 3). The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 28.8 min., τ minor = 24.4 min. (87.5:2.5 er). 9c N-((2S,3R)-2-Hydroxy-,-dimethoxyheptan-3-yl)-2-nitrobenzene-- sulfonamide (Table 3, entry 3) Following the general procedure, pure diastereomer syn-9c was isolated by FC on silica gel (eluent: hexanes:acetone 80:20) as a brown viscous oil (25 mg, 66% yield). H NMR (700 MHz, CDCl 3) δ: (m, H), (m, H), 7.72 (pd, J = 7.5,.7 Hz, 2H), 5.69 (d, J = 8.5 Hz, H), 4.29 (d, J = 7.5 Hz, H), 3.7 (q, J = 7.0 Hz, H), 3.5 (dd, J = 7.6,.6 Hz, H), 3.4 (s, 3H), 3.40 (s, 3H), 2.33 (m, H), (m, H), (m, H),.20.0 (m, 4H), 0.73 (t, J = 6.9 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 47.9, 35.9, 33.3, 32.9, 30.5, 25.3, 04.5, 7.6, 56.3, 55.0, 55.0, 54.9, 32.7, 28.2, 22.4, 4.0. HRMS calculated for [C 5H 24N 2O 7S+H + ]: ; found: [α] D = 72.5 (c =.0, CHCl 3). The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 36.2 min, τ minor = 28.0 min, (90:0 er). 9d N-((2S,3R)-2-Hydroxy-,-dimethoxyhexan-3-yl)-2-nitrobenzene-- sulfonamide (Table 3, entry 4) Following the general procedure, pure diastereomer syn-9d was isolated by FC on silica gel (eluent: hexanes:acetone, 80:20 as a light brown viscous oil ) (8 mg, 49% yield). H NMR (700 MHz, CDCl 3) δ: 8.5 (dd, J = 7.4,.7 Hz, H), 7.86 (dd, J = 7.6,.6 Hz, H), 7.72 (pd, J = 7.5,.6 Hz, 2H), 5.7 (d, J = 9.4 Hz, H), 4.26 (d, J = 7.5 Hz, H), 3.72 (dtd, J = 9.0, 7.3,.6 Hz, H), 3.50 (dd, J = 7.6,.7 Hz, H), 3.40 (s, 3H), 3.38 (s, 3H), 2.39 (bs, H), (m, H), (m, H),.28.4 (m, 2H), 0.78 (t, J = 7.4 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 47.9, 35.8, 33.4, 32.9, 30.5, 25.3, 04.4, 7.5, 56., 54.9, 54.6, 35., 9.2, 3.8. HRMS calculated for [C 4H 22N 2O 7S+H + 22 ]: ; found: [α] D = (c =.0, CHCl 3) The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 59.3 min., τ minor = 53.2 min. (88.5:.5 er). 9e N-((2R,3S)-2-Hydroxy-,-dimethoxypentan-3-yl)-2-nitrobenzene-- sulfonamide (Table 3, entry 5) Following the modified general procedure (aziridination performed using ent-5b as catalyst) pure diastereomer syn-9e was isolated by FC on silica gel (eluent: hexanes:acetone 4:) as a light brown viscous oil (2 mg, 34% yield). H NMR (700 MHz, CDCl 3) δ: (m, H), (m, H), (m, 2H), 5.7 (d, J = 9.3 Hz, H), 4.27 (d, J = 7.5 Hz, H), 3.64 (dtd, J = 9., 7.3,.6 Hz, H), 3.54 (dd, J = 7.5,.6 Hz, H), 3.4 (s, 3H), 3.40 (s, 3H), 2.34 (bs, H), (m, H), (m, H), 0.79 (t, J = 7.5 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 47.9, 35.9, 33.3, 32.9, 30.5, 25.3, 04.5, 7.3, 56.3, 56.2, 55.00, 26.2, 0.7. HRMS calculated for [C 3H 20N 2O 7S+H + 22 ]: ; found: [α] D = 62.2 (c =.0, CHCl 3) The er was determined by HPLC using a chiral Chiralpack IA column [hexane:i-proh, 90:0]; column temperature 30 C; flow rate.0 ml/min; τ major = 25.0 min., τ minor = 32.9 min. (0.5:89.5 er). S9

10 9f N-((2R,3S)-3-Hydroxy-4,4-dimethoxy--phenylbutan-2-yl)-2-nitrobenzene-- sulfonamide (Table 3, entry 6) Following the general procedure, pure diastereomer syn-9f was isolated by FC on silica gel (eluent: hexanes:acetone 80:20) as a brown viscous oil (8 mg, 45% yield). H NMR (700 MHz, CDCl 3) δ: 7.85 (dd, J = 7.8,.5 Hz, H), 7.80 (dd, J = 7.8,.4 Hz, H), 7.6 (td, J = 7.7,.5 Hz, H), 7.58 (td, J = 7.6,.4 Hz, H), 7.06 (d, J = 4.3 Hz, 4H), (m, H), 5.79 (d, J = 9.4 Hz, H), 4.38 (d, J = 7.5 Hz, H), 4.04 (dtd, J = 9.3, 7.9,.3 Hz, H), 3.5 (dt, J = 7.6,.5 Hz, H), 3.42 (s, 3H), 3.36 (s, 3H), 2.89 (dd, J = 3.7, 7.8 Hz, H), 2.77 (dd, J = 3.7, 7.9 Hz, H), (m, H). 3 C NMR (76 MHz, CDCl 3) δ: 47.5, 37.4, 35.8, 33., 32.9, 30.2, 29.4 (2C), 28.5 (2C), 26.9, 25.3, 04.4, 7., 56.7, 56.0, 55.2, HRMS calculated for [C 8H 22N 2O 7S+H + ]: 4.20; found: 4.. [α] D 2 = -8,5 (c =.0, CHCl 3). The er was determined by HPLC using a chiral Chiralpack IA column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 8.9 min., τ minor = 2.6 min. (92.5:7.5 er). 9g N-((2R,3S)--(Benzyloxy)-3-hydroxy-4,4-dimethoxybutan-2-yl)-2- nitrobenzene--sulfonamide (Table 3, entry 7) Following the general procedure, pure diastereomer syn-9g was isolated by FC on silica gel (eluent: hexanes:acetone, 80:20) in as a pale yellow viscous oil (20 mg, 46% yield). H NMR (700 MHz, CDCl 3) δ: (m, H), (m, H), 7.56 (m, 2H), (m, 3H), (m, 2H), 5.92 (d, J = 8.3 Hz, H), 4.34 (d, J = 7.4 Hz, H), 4.28 (d, J =.8 Hz, H), 4.22 (d, J =.8 Hz, H), 3.94 (m, H), 3.70 (dd, J = 7.4,.4 Hz, H), 3.52 (d, J = 5.8 Hz, 2H), 3.4 (s, 3H), 3.37 (s, 3H), 2.57 (bs, H). 3 C NMR (76 MHz, CDCl 3) δ: 47.7, 37.5, 35.6, 33., 32.7, 30.8, 28.5 (2C), 27.9, 27.8 (2C), 25.2, 04., 73.4, 7.2, 70.7, 56.3, 54.8, HRMS calculated for [C 9H 24N 2O 8S+H + 25 ]: ; found: [α] D = (c = 0.85, CHCl 3). The er was determined by HPLC using a chiral Chiralpack IA column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 5.5 min., τ minor = 3.9 min. (89.5:0.5 er). 9h N-((2S,3R,Z)-2-Hydroxy-,-dimethoxynon-6-en-3-yl)-2- nitrobenzenesulfo--namide (Table 4, entry 8) Following the general procedure, pure diastereomer syn-9h was isolated by FC on silica gel (eluent: hexanes:acetone, 80:20) in as a light brown viscous oil (20 mg, 50% yield). H NMR (700 MHz, CDCl 3) δ: 8.5 (dd, J = 7.3,.9 Hz, H), 7.86 (dd, J = 7.4,.8 Hz, H), 7.72 (pd, J = 7.5,.7 Hz, 2H), 5.72 (d, J = 9.5 Hz, H), 5.3 (dtt, J = 0.4, 7.3,.5 Hz, H), 5.3 (dtt, J = 0.6, 7.2,.6 Hz, H), 4.29 (d, J = 7.5 Hz, H), 3.73 (td, J = 7.7, 5.9 Hz, H), 3.52 (dt, J = 7.6,.7 Hz, H), 3.4 (s, 3H), 3.40 (s, 3H), 2.37 (bs, H), (m, H),.9.84 (m, 3H),.69 (dddd, J = 3.2, 9.6, 7.4, 5.5 Hz, H),.43 (ddt, J = 3.5, 9.7, 6.7 Hz, H), 0.87 (t, J = 7.5 Hz, 3H). 3 C NMR (76 MHz, CDCl 3) δ: 47.9, 35.8, 33.4, 32.9, 32.8, 30.5, 27.4, 25.3, 04.5, 7.5, 56.3, 55.0, 54.6, 33.0, 23.7, 20.6, 4.4. HRMS calculated for [C 7H 26N 2O 7S+H + 27 ]: ; found: [α] D = (c =.0, CHCl 3) The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i- PrOH, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 27.5 min., τ minor = 2.0 min. (90:0 er). S0

11 4. Organocatalytic cis-aziridination of α,β-unsaturated aldehydes 2 mechanistic experiments 4.. Organocatalytic cis-aziridination of α,β-unsaturated aldehydes 2 pyrrolidine-promoted PRI In an ordinary 4 ml glass vial, equipped with a Teflon-coated magnetic stirring bar and a screw cap, catalyst 5a (0.2 equiv, 0.02 mmol, 2.0 mg), sodium acetate (.5 equiv, 0.5 mmol, 2.3 mg), NsNHOTs 3a ( equiv, 0. mmol, 34. mg) and trans-2-nonenal (.5 equiv, 0.5 mmol, 24.8 μl) were dissolved in CH 2Cl 2 (0.8 ml) and stirring was maintained for 3 h at ambient temperature. When the trans-selective aziridination reaction was accomplished (the reaction progress was monitored by H NMR), the reaction mixture was cooled to -40 o C and pyrrolidine (0. equiv, 0.0 mmol, 0.82 μl) was added. The progress of PRI was monitored by H NMR. Pure cis-diastereomer was isolated by flash chromatography on silica gel (eluent: CH 2Cl 2). In order to determine the er, the product was converted to the alcohol h. Notably, aziridination of 2-methylpent-2-enal was attempted according to the general procedure for the organocatalytic cis-aziridination of α,β-unsaturated aldehydes 2 described at page S3. No PRI was observed in this case. S

12 4.2. Organocatalytic cis-aziridination of α,β-unsaturated aldehydes 2 experiment with D 2O In an ordinary 4 ml glass vial, equipped with a Teflon-coated magnetic stirring bar and a screw cap, catalyst 5b (0.2 equiv, 0.02 mmol, 6.5 mg), sodium acetate (.5 equiv, 0.5 mmol, 2.3 mg), NsNHOTs 3a ( equiv, 0. mmol, 37.2mg) and trans-2-nonenal (.5 equiv, 0.5 mmol, 24.8 μl) were dissolved in CH2Cl2 (0.8 ml) and D2O (2.7 equiv, 0.28 mmol, 5μL) was added. Stirring was maintained for 6 h at ambient temperature and the progress of the incorporation of the deuterium was determined by H NMR. H NMR S2

13 Comparison of H NMR spectrum of a (top) and in a mixture with 0a (bottom) (expansions of ppm and ppm regions) S3

14 Diastereoisomeric excess [%] Signal integration [ar.val.] 4.3. Organocatalytic cis-aziridination of α,β-unsaturated aldehydes 2 monitoring of the reaction progress 0,7 0,6 0,5 0,4 0,3 0,2 0, Time [h] Cis isomer Trans isomer Time [h] S4

15 5. Assignment of the absolute configuration In an ordinary 4 ml glass vial, equipped with a Teflon-coated magnetic stirring bar and a screw cap, catalyst 5b (0.2 equiv, 0.02 mmol, 6.5 mg), sodium acetate (.5 equiv, 0.5 mmol, 2.3 mg), TsNHOTs 3c ( equiv, 0. mmol) and the aldehyde 2h (.5 equiv, 0.5 mmol) were dissolved in CH 2Cl 2 (0.8 ml) and stirring was maintained for 3 h at ambient temperature. Pure product cis-j was isolated by flash chromatography on silica gel (eluent: CH 2Cl 2) and directly subjected to the reduction using the following procedure. In an ordinary 4 ml glass vial, equipped with a Teflon-coated magnetic stirring bar and a screw cap, aziridine cis-j ( equiv, 0.05 mmol) was dissolved in a glacial acetic acid (0,4 ml) and the resulting solution was cooled in cold water bath. Subsequently, sodium borohydride (5 equiv, 9.5 mg) was added, and reaction was stirred for 30 min. at room temperature. Reaction was quenched with water (5 ml), extracted with dichloromethane (3 x 0 ml). Combined organic layers were washed with saturated aqueous solution of sodium bicarbonate ( x 5 ml) and water ( x 5 ml), dried over anhydrous MgSO 4, filtered and concentrated in vacuo. Pure product j was isolated by flash chromatography on silica gel (eluent: hexane:acetone 80:20). j ((2R,3S)-3-((Benzyloxy)methyl)-- ((4-methylbenzene--sulfonyl)aziridin-2-yl)methanol. H NMR (700 MHz, CD 3OD) δ: 7.82 (d, J = 8.2 Hz, 2H), 7.37 (d, J = 8.0 Hz, 2H), (m, 3H), (m, 2H), 4.82 (s, 2H), 4.40 (s, 2H), 3.69 (dd, J =.4, 3.9 Hz, H), (m, 2H), 3.46 (dd, J =.4, 7. Hz, H), 3.3 (p, J =.6 Hz, H), (m, 2H), 2.4 (s, 3H). 3 C NMR (76 MHz, CD 3OD) δ: 46.3, 39.3, 36., 30.8, 29.3 (2C), 29.2 (2C), 28.7 (2C), 28.7, 73.8, 67.7, 59.8, 44.7, 44.4, 2.6. HRMS calculated for [C 8H 2NO 4S+H + ]: ; found: [α] D 2 = 20.8 (c =.0, CHCl 3). The er was determined by HPLC using a chiral Chiralpack ID column [hexane:i-proh, 80:20]; column temperature 30 C; flow rate.0 ml/min; τ major = 23.2 min., τ minor = 25.2 min. (90:0 er). S5

16 6. NMR data cis-a (2R,3R)-3-Hexyl--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry ) H NMR 3 C NMR S6

17 a ((2R,3R)-3-Hexyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR 3 C NMR S7

18 cis-b (2R,3R)--((2-Nitrobenzene--sulfonyl)-3-pentylaziridine-2-carbaldehyde (Table 2, entry 2) H NMR 3 C NMR S8

19 b ((2R,3R)--(2-Nitrobenzene--sulfonyl)-3-pentylaziridin-2-yl)methanol H NMR 3 C NMR S9

20 cis-c (2R,3R)-3-Butyl--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 3) H NMR 3 C NMR S20

21 c ((2R,3R)-3-Butyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR 3 C NMR S2

22 cis-d (2R,3R)--((2-Nitrobenzene--sulfonyl)-3-propylaziridine-2-carbaldehyde (Table 2, entry 4) H NMR 3 C NMR S22

23 d ((2R,3R)--((2-Nitrobenzene--sulfonyl)-3-propylaziridin-2-yl)methanol H NMR 3 C NMR S23

24 cis-e (2S,3S)-3-Ethyl--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 5) H NMR 3 C NMR S24

25 e ((2S,3S)-3-Ethyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR 3 C NMR S25

26 cis-f (2R,3R)-3-Methyl--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 6) H NMR 3 C NMR S26

27 f ((2R,3R)-3-Methyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR 3 C NMR S27

28 cis-g (2R,3R)-3-Benzyl--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 7) H NMR 3 C NMR S28

29 g ((2R,3R)-3-Benzyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR 3 C NMR S29

30 cis-h (2R,3S)-3-((Benzyloxy)methyl)--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 8) H NMR 3 C NMR S30

31 h ((2R,3S)-3-((Benzyloxy)methyl)--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR 3 C NMR S3

32 cis-i (2R,3R)-3-((Z)-Hex-3-en--yl)--((2-nitrobenzene--sulfonyl)aziridine-2-carbaldehyde (Table 2, entry 9) H NMR 3 C NMR S32

33 i ((2R,3R)-3-((Z)-Hex-3-en--yl)--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol H NMR 3 C NMR S33

34 j ((2R,3S)-3-((Benzyloxy)methyl)--((4-methylbenzene--sulfonyl)aziridin-2-yl)methanol (Scheme 3) H NMR 3 C NMR S34

35 9a N-((2S,3R)-2-Hydroxy-,-dimethoxynonan-3-yl)-2-nitrobenzene--sulfonamide (Table 3, entry ) H NMR 3 C NMR S35

36 9b N-((2S,3R)-2-Hydroxy-,-dimethoxyoctan-3-yl)-2-nitrobenzene--sulfonamide sulfonamide (Table 3, entry 2) H NMR 3 C NMR S36

37 9c N-((2S,3R)-2-Hydroxy-,-dimethoxyheptan-3-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 3) H NMR 3 C NMR S37

38 9d N-((2S,3R)-2-Hydroxy-,-dimethoxyhexan-3-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 4) H NMR 3 C NMR S38

39 9e N-((2R,3S)-2-Hydroxy-,-dimethoxypentan-3-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 5) H NMR 3 C NM S39

40 9f N-((2R,3S)-3-Hydroxy-4,4-dimethoxy--phenylbutan-2-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 6) H NMR 3 C NMR S40

41 9g N-((2R,3S)--(Benzyloxy)-3-hydroxy-4,4-dimethoxybutan-2-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 7) H NMR 3 C NMR S4

42 9h N-((2S,3R,Z)-2-Hydroxy-,-dimethoxynon-6-en-3-yl)-2-nitrobenzenesulfo--namide (Table 3, entry 8) H NMR 3 C NMR S42

43 7. HPLC traces a ((2R,3R)-3-Hexyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol Racemic sample Enantiomerically enriched sample S43

44 b ((2R,3R)--(2-Nitrobenzene--sulfonyl)-3-pentylaziridin-2-yl)methanol Racemic sample Enantiomerically enriched sample S44

45 c ((2R,3R)-3-Butyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol Racemic sample Enantiomerically enriched sample S45

46 d ((2R,3R)--((2-Nitrobenzene--sulfonyl)-3-propylaziridin-2-yl)methanol Racemic sample Enantiomerically enriched sample S46

47 e ((2S,3S)-3-Ethyl--((2-Nitrobenzene--sulfonyl)aziridin-2-yl)methanol Racemic sample Enantiomerically enriched sample S47

48 f ((2R,3R)-3-Methyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol Racemic sample Enantiomerically enriched sample S48

49 g ((2R,3R)-3-Benzyl--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol Racemic sample Enantiomerically enriched sample S49

50 h ((2R,3S)-3-((Benzyloxy)methyl)--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol Racemic sample Enantiomerically enriched sample S50

51 i ((2R,3R)-3-((Z)-Hex-3-en--yl)--((2-nitrobenzene--sulfonyl)aziridin-2-yl)methanol Racemic sample Enantiomerically enriched sample S5

52 j ((2R,3S)-3-((Benzyloxy)methyl)--((4-methylbenzene--sulfonyl)aziridin-2-yl)methanol (Scheme 3) Racemic sample Enantiomerically enriched sample S52

53 9a N-((2S,3R)-2-Hydroxy-,-dimethoxynonan-3-yl)-2-nitrobenzene--sulfonamide (Table 3, entry ) Racemic sample Enantiomerically enriched sample S53

54 9b N-((2S,3R)-2-Hydroxy-,-dimethoxyoctan-3-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 2) Racemic sample Enantiomerically enriched sample S54

55 9c N-((2S,3R)-2-Hydroxy-,-dimethoxyheptan-3-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 3) Racemic sample Enantiomerically enriched sample S55

56 9d N-((2S,3R)-2-Hydroxy-,-dimethoxyhexan-3-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 4) Racemic sample Enantiomerically enriched sample S56

57 9e N-((2R,3S)-2-Hydroxy-,-dimethoxypentan-3-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 5) Racemic sample Enantiomerically enriched sample S57

58 9f N-((2R,3S)-3-Hydroxy-4,4-dimethoxy--phenylbutan-2-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 6) Racemic sample Enantiomerically enriched sample S58

59 9g N-((2R,3S)--(Benzyloxy)-3-hydroxy-4,4-dimethoxybutan-2-yl)-2-nitrobenzene--sulfonamide (Table 3, entry 7) Racemic sample Enantiomerically enriched sample S59

60 9h N-((2S,3R,Z)-2-hydroxy-,-dimethoxynon-6-en-3-yl)-2-nitrobenzenesulfo--namide (Table 3, entry 8) Racemic sample Enantiomerically enriched sample S60