Experimental and data

Z- and E-(1RS,2RS)-1-Epoxy-1-phenylhept-3-ene, 2b

Butyllithium (1.6 mol dm-3, 2.5 ml, 4.0 mmol) was added dropwise to n-butyltriphenylphosphonium bromide (1.61 g, 4.03 mmol) in THF (6 ml) under argon at 0 °C. This was added to the aldehyde 1 (597 mg, 4.03 mmol) in THF (7 ml) under argon at 0 °C. After 30 min, methanol (4 ml) was added followed by water (20 ml) and CH2Cl2(20 ml). The organic phase was separated and the aqueous phase was extracted with CH2Cl2 (2 x 10 ml). The organic phases were dried (MgSO4), filtered and the solvent evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel, eluting with ethyl acetate-light petroleum (bp 40-60 °C) (20:1) to give the vinyl epoxide 2b (450 mg, 60%, 5:2, Z:E) as a colourless oil, Rf 0.67 (hexane-ethyl acetate, 6:1); IR: (CHCl3)/ cm-1 1665 (Z alkene), 1655 (E alkene), 1605 and 1495 (Ph)

1H NMR: (250 MHz; CDCl3) 7.41-7.23 (10H, m, 2xPh, E and Z), 5.98 (1H, dt, J 15 and 7, CHCH2, E), 5.79 (1H, dtd, J 10.5, 7.5 and 0.5, CHCH2, Z), 5.35 (1H, ddt, J 15, 8 and 1, CH=CHCH2, E), 5.24 (1H, ddt, J 10.5, 8.5 and 1, CH=CHCH2, Z), 3.78 (1H, d, J 2, PhCH, Z), 3.77 (1H, d, J 2, PhCH, E), 3.60 (1H, ddd, J 8.5, 2 and 0.5, PhCHCH, Z), 3.34 (1H, dd, J 8 and 2, PhCHCH, E), 2.34-2.05 (4H, m, 2 x CHCH2, E and Z), 1.46 (4H, sext, J 7.5, CH2CH3, E and Z), 0.95 (3H, t, J 7.5, CH2CH3, E) and 0.94 (3H, t, J 7.5, CH2CH3, Z); 13C NMR: (62.9 MHz; CDCl3) 137.47 (C), 136.96 (CH), 136.90 (CH), 128.48 (CH), 128.44 (CH), 128.09 (CH), 128.05 (CH), 127.11 (CH), 126.74 (CH), 125.50 (CH), 62.94 (CH), 60.21 (CH), 59.89 (CH), 58.67 (CH), 34.40 (CH2), 29.85 (CH2), 22.69 (CH2), 22.08 (CH2) and 13.58 (CH3)

(Found: M+, 188.1208. C13H16O requires M, 188.1201) m/z 188 (1.3%, M), 159 (23.8, M - C2H5), 145 (49.4, M - C3H7), 117 (100) and 77 (35.2, C6H5).

(3RS,4SR)-1-Azido-2-hydroxy-1-phenylbut-3-ene, 3a, (3RS,4SR)-2-Azido-1-hydroxy-1-phenylbut-3-ene, 4a and 4-Azido-1-hydroxy-1-phenylbut-2-ene, 5a.

Sodium azide (195 mg, 3.0 mmol) and NH4Cl (155 mg, 2.9 mmol) were added to the epoxide 2a (192 mg, 1.32 mmol) in MeOH/water (4:1, 8 ml) at room temp. under nitrogen. The mixture was refluxed for 2.5 h and then allowed to stir at room temp. for 16 h before water (20 ml) and CH2Cl2 (20 ml) were added. The organic layer was separated and the aqueous layer was extracted with CH2Cl2 (2 x 20 ml). The organic extracts were combined and washed with brine (20 ml), dried (MgSO4), filtered and the solvent evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel, eluting with ethyl acetate-light petroleum (bp 40-60 °C) (1:7) to give a mixture of azido-alcohols:

3a: (50 mg, 20%), Rf 0.14 (hexane-ethyl acetate, 8:1); IR: (CHCl3)/cm-1 3605 (OH), 2110 (N3), 1600 and 1490 (Ph); 1H NMR: (250 MHz; CDCl3) 7.48-7.28 (5H, m, aromatic CH), 5.87 (1H, ddd, J 16, 10 and 6, CHCH2), 5.31 (1H, bd, J 16, CH=CHAHB, E), 5.25 (1H, bd, J 10, CH=CHAHB, Z), 4.60 (1H, d, J 6, PhCH), 4.37-4.28 (1H, bm, CHOH) and 1.94 (1H, d, J 4, OH)

13C NMR: (62.9 MHz; CDCl3) 135.94 (C), 135.86 (CHCH2), 128.72 (CH), 128.61 (CH), 127.89 (CH), 118.00 (CHCH2), 75.60 (CH) and 70.19 (CH); (Found: M+, 189.0892. C10H11N3O requires M, 189.0902) m/z 189 (0.4%, M), 161 (0.8, M - N2) and 57 (100).

4a: (48 mg, 19%), Rf 0.18 (hexane-ethyl acetate, 8:1); 1H NMR: (250 MHz; CDCl3) 7.42-7.22 (5H, m, aromatic CH), 5.75 (1H, ddd, J 16, 10 and 6, CHCH2), 5.40-5.20 (2H, m, CH2), 4.75 (1H, d, J 6, PhCH), 4.18-4.07 (1H, m, CHN3) and 2.65 (1H, s, OH).

5a: (102 mg, 41%), Rf 0.07 (hexane-ethyl acetate, 8:1)

IR: (CHCl3)/cm-1 3605 (OH), 2105 (N3), 1600 and 1490 (Ph); 1H NMR: (250 MHz; CDCl3) 7.40-7.22 (5H, m, aromatic CH), 6.00 (1H, dd, J 15 and 5.5, PhCHCH), 5.84 (1H, dtd, J 15, 6 and 1, CHCH2), 5.25 (1H, d, J 5.5, PhCH), 3.85 (2H, d, J 6, CH2) and 2.22 (1H, s, OH); 13C NMR: (62.9 MHz, CDCl3) 142.34 (C), 137.26 (CH), 128.69 (CH), 127.99 (CH), 126.34 (CH), 124.03 (CH), 74.14 (CH) and 52.11 (CH2); (Found: M+, 189.0906. C10H11N3O requires M, 189.0902) m/z 189 (0.5%, M), 161 (0.6, M - N2) and 105 (100).

(1RS,2SR)-1-Azido-2-hydroxy-1-phenylhept-3-ene, 3b, (1RS,2SR)-2-Azido-1-hydroxy-1-phenylhept-3-ene, 4b and (1RS,4RS)-4-Azido-1-hydroxy-1-phenylhept-2-ene, 5b

In the same way as the azido-alcohols 3-5a, sodium azide (195 mg, 3.0 mmol) and the epoxide 2b (327 mg, 1.74 mmol) gave a mixture of azidoalcohols 3b and 4b (E and Z) and 5b (362 mg, 90%) as an inseparable mixture as an oil, Rf 0.25 and 0.23 (hexane-ethyl acetate, 6:1); IR: (CHCl3)/cm-1 3605 (OH), 2110 (N3), 1605 and 1495 (Ph); 1H NMR: (250 MHz; CDCl3) 7.45-7.25 (15H, m, aromatic CH, 3b, 4b and 5b), 5.94 (1H, ddd, J 15.5, 6 and 1, PhCHCH, 5b), 5.80-5.20 (5H, m, 2 x CH=CH, 3b and 4b, CHCHN3, 5b), 4.70-3.80 (6H, m, 3 x CHOH and 3 x CHN3, 3b, 4b and 5b), 2.70 (1H, bs, OH), 2.45 (1H, bs, OH), 2.18 (1H, bs, OH), 2.17-1.95 (4H, m, 2 x CHCH2, 3b and 4b), 1.63-1.25 (8H, m, 2 x CH2CH3, 3b and 4b, CH2CH2, 5b] and 1.00-0.75 (9H, m, 3 x CH3, 3b, 4b and 5b); (Found: M+, 231.1371. C13H17N3O requires M, 231.1372) m/z 231 (11.2%, M) and 203 (100, M - N2).

Data for azido-alcohols 3-4c is given in ref. 10.

(4RS,5RS)-1-Azido-2-hydroxy-4-methyl-1-phenylpent-3-ene, 3d, (4RS,5RS)-2-Azido-1-hydroxy-4-methyl-1-phenylpent-3-ene, 4d and 4-Azido-1-hydroxy-4-methyl-1-phenylpent-2-ene, 5d

In the same way as the azido-alcohols 3-5a, sodium azide (780 mg, 12.0 mmol) and epoxide 2d (924 mg, 5.3 mmol) gave the azido-alcohols 3-5d (940 mg, 82%, 1:1:1) as an oil, Rf 0.20 (hexane-ethyl acetate, 7:1); IR: (CHCl3)/cm-1 3605 (OH), 2110 (N3), 1605 and 1495 (Ph); 1H NMR: (300 MHz; CDCl3) 7.40-7.20 (15H, m, 3 x Ph), 5.96-5.80 (2H, m, CH=CH, 5d), 5.26 (1H, dsept, J 9.5 and 1, C=CH, 3d or 4d), 5.19 (1H, d, J 5, PhCH, 3d), 5.16 (1H, dsept, J 9.5 and 1, C=CH, 3d or 4d), 4.66 (1H, dd, J 5 and 3, PhCH, 4d or 5d), 4.52 (1H, dd, J 7.5 and 3, PhCH, 4d or 5d), 4.40-4.30 [2H, m, CHOH (3d) and CHN3 (4d)], 2.66 (1H, d, J 3, OH, 5d), 2.32 (1H, d, J 3, OH, 4d), 2.05 (1H, d, J 3.5, OH, 3d), 1.80 (3H, d, J 1, CH3, 4d), 1.70 (3H, d, J 1, CH3, 3d), 1.59 (3H, d, J 1, CH3, 4d), 1.42 (3H, d, J 1, CH3, 3d) and 1.37 [6H, s, C(CH3)2, 5d]; 13C NMR: (75.5 MHz; CDCl3) 142.58 (C), 141.26 (C), 140.50 (C), 140.08 (C), 139.95 (C), 134.20 (CH), 131.92 (CH), 128.65 (CH), 128.23 (CH), 128.20 (CH), 128.06 (CH), 128.01 (CH), 127.88 (CH), 126.87 (CH), 126.77 (CH), 126.35 (CH), 118.44 (CH), 117.78 (CH), 76.54 (CH), 75.94 (CH), 74.29 (CH), 66.20 (CH), 64.97 (CH), 61.43 (C), 26.49 (CH3), 25.78 (CH3), 25.80 (CH3), 18.48 (CH3) and 18.29 (CH3); (Found: M+, 217.1206. C12H15N3O requires M, 217.1215); m/z 217 (0.2%, M), 189 (1.2, M - N2) and 105 (100).

(2RS,3RS)-2-Phenyl-3-vinylaziridine, 6a

Triphenylphosphine (155 mg, 0.58 mmol) was added to the azido-alcohols 3a and 4a (110 mg, 0.58 mmol) in MeCN (5 ml) under argon at room temperature. The mixture was refluxed for 2 h before the solvent was evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel, eluting with ethyl acetate-hexane (1:5) to give the aziridine 6a (56 mg, 66%) as an oil, Rf 0.28 (hexane-ethyl acetate, 4:1); IR: (CHCl3)/cm-1 3305 (NH), 1635 (C=C), 1605 and 1495 (Ph); 1H NMR: (250 MHz; CDCl3) 7.40-7.20 (5H, m, Ph), 6.30-6.12 (1H, bm, CH=CH2), 5.97 (1H, dd, J 17 and 1, CH=CHAHB), 5.79 (1H, dd, J 10 and 1, CH=CHAHB), 2.95 (1H, bs, PhCH), 2.55 (1H, bs, PhCHCH) and 1.08 (1H, bs, NH); (Found: M+, 145.0884. C10H11N requires M, 145.0891); m/z 145 (28.6%, M), 117 (34.9, C8H7N).

Z- and E-(2RS,3SR)-2-(Pent-1-enyl)-3-phenylaziridine, 6b

In the same way as the aziridine 6a, triphenylphosphine (400 mg, 1.5 mmol) and azido-alcohols 3-5b (326 mg, 0.58 mmol) gave the aziridine 6b [53 mg, 34%, 3:2, E:Z (based on deduction of 40% of azido-alcohol 5b)] as an oil, Rf 0.21 (hexane-ethyl acetate, 7:1); IR: (CHCl3)/cm-1 3305 (NH), 1605 and 1495 (Ph); 1H NMR: (250 MHz; CDCl3) 7.39 (10H, m, 2 x Ph), 5.78 (1H, dt, J 15 and 7, CHCH2, E), 5.61 (1H, dt, J 10.5 and 7, CHCH2, Z), 5.18 (1H, ddt, J 15, 8 and 1.5, CHCH=CH, E), 5.01 (1H, ddt, J 10.5, 9 and 1.5, CHCH=CH, Z), 2.92 (1H, d, J 2.5, PhCH, Z), 2.90 (1H, d, J 2.5, PhCH, E), 2.70 (1H, dd, J 9 and 2.5, CHCH=CH, Z), 2.50 (1H, dd, J 8 and 2.5, CHCH=CH, E), 2.24-1.98 (4H, m, 2 x CHCH2), 1.52-1.34 (4H, m, 2 x CH2CH3), 1.21 (2H, bs, NH), 0.92 (6H, t, J 7, 2 x CH3); 13C NMR: (62.9 MHz; CDCl3) 139.87 (2 x C), 133.74 (CH), 133.28 (CH), 129.87 (CH), 129.69 (CH), 128.39 (CH), 127.02 (CH), 126.98 (CH), 125.75 (CH), 125.65 (CH), 43.41 (CH), 40.76 (2 x CH), 39.49 (CH), 34.43 (CH2), 29.81 (CH2), 22.75 (CH2), 22.32 (CH2), 13.61 (CH3) and 13.57 (CH3); (Found: M+, 187.1370. C13H17N requires M, 187.1361); m/z 187 (13.6%, M) 172 (7.0, M - CH3), 158 (39.6, M - CH5) and 144 (100, C10H10N).