1H NMR spectroscopy) of hydroxy aziridines cis-61 and trans-61.
Purification by flash chromatography on silica with petrol–Et2O
(1 : 4) as eluent gave hydroxy aziridine trans-61 (82 mg, 12%) as
CHAHBCH CH2), 2.89 (dd, J = 15.0, 7.0, 1H, CHAHBCH CH2),
2.42 (s, 3H, Me), 2.04 (dd, J = 14.0, 8.5, 1H, CH), 1.91 (dt, J =
13.0, 8.0, 1H, CH), 1.67 (ddd, J = 14.0, 10.5, 8.0, 1H, CH), 1.26–
1.12 (m, 2H, CH and OH); 13C NMR (100.6 MHz, CDCl3) d
=
=
1
a colourless oil, RF(1 : 4 petrol–Et2O) 0.2; H NMR (400 MHz,
=
CDCl3) d 7.80 (d, J = 8.0, 2H, m-C6H4Me), 7.30 (d, J = 8.0, 2H,
o-C6H4Me), 4.30 (d, J = 4.5, 1H, CHO), 3.32 (s, 1H, CHN), 2.44
(s, 3H, Me), 2.35–2.23 (m, 1H, CH), 1.96–1.93 (m, 1H, CH), 1.83
(s, 3H, Me), 1.63–1.56 (m, 2H, CH and OH), 1.25–1.14 (m, 1H,
CH); 13C NMR (100.6 MHz, CDCl3) d 143.8 (ipso-C6H4SO2),
137.8 (ipso-C6H4Me), 129.5 (m-C6H4Me), 127.2 (o-C6H4Me),
72.9 (CHO), 58.2 (CN), 54.6 (CHN), 32.6 (CH2), 31.4 (CH2),
21.6 (Me), 14.9 (Me); MS (CI, NH3) m/z 285 [(M + NH4)+, 100],
268 (12), 250 (21), 189 (55), 112 (100); HRMS (CI, NH3) m/z:
[M + NH4]+ calcd for C13H17NO3S, 285.1272; found, 285.1273
and hydroxy aziridine cis-61 (446 mg, 63%) as a white solid,
mp 104–107 ◦C; RF(1 : 4 petrol–Et2O) 0.2; IR (CDCl3) 3600
144.0 (ipso-C6H4SO2), 137.6 (ipso-C6H4Me), 133.3 ( CH), 129.6
(m-C6H4Me), 127.1 (o-C6H4Me), 118.6 ( CH2), 73.0 (CHO), 60.1
(CN), 54.7 (CHN), 33.7 (CH2), 29.9 (CH2), 29.3 (CH2), 21.6 (Me);
MS (CI, NH3) m/z 311 [(M + NH4)+, 20], 294 (100), 276 (30),
138 (35); HRMS (CI, NH3) m/z: [M + H]+ calcd for C15H19NO3S,
294.1164; found, 294.1162.
=
5-(3-Butenyl)-6-[(4-methylphenyl)sulfonyl]-6-azabicyclo[3.1.0]-
hexan-2-ol trans-63 and cis-63. Using the general procedure,
allylic alcohol 38 (355 mg, 2.6 mmol), chloramine-T trihydrate
(796 mg, 2.8 mmol) and PhMe3NBr3 (97 mg, 0.3 mmol) in MeCN
(12 mL) gave the crude product, which contained a 75 : 25 mixture
(by 1H NMR spectroscopy) of hydroxy aziridines cis-63 and trans-
63. Purification by flash chromatography on silica with hexane–
1
(OH), 1321 (SO2), 1159 (SO2), 1092 cm-1; H NMR (400 MHz,
CDCl3) d 7.86 (d, J = 8.0, 2H, m-C6H4Me), 7.33 (d, J = 8.0, 2H,
o-C6H4Me), 4.29 (dtd, J = 10.0, 8.0, 3.0, 1H, CHO), 3.44 (d, J =
3.0, 1H, CHN), 2.44 (s, 3H, Me), 2.15 (dd, J = 14.0, 8.0, 1H, CH),
1.95 (dt, J = 13.5, 8.0, 1H, CH), 1.83 (s, 3H, Me), 1.60 (ddd, J =
14.0, 10.5, 8.0, 1H, CH), 1.20 (ddt, J = 13.5, 10.5, 8.0, 1H, CH),
1.06 (d, J = 10.0, 1H, OH); 13C NMR (100.6 MHz, CDCl3) d
144.0 (ipso-C6H4SO2), 137.8 (ipso-C6H4Me), 129.6 (m-C6H4Me),
127.1 (o-C6H4Me), 73.1 (CHO), 57.3 (CN), 55.8 (CHN), 33.4
(CH2), 29.8 (CH2), 21.6 (Me), 15.3 (Me); MS (CI, NH3) m/z
268 [(M + H)+, 26], 250 (16), 112 (100); HRMS (CI, NH3) m/z:
[M + H]+ calcd for C13H17NO3S, 268.1004; found, 268.1007.
1
EtOAc (2 : 1) as eluent gave a 65 : 35 mixture (by H NMR
spectroscopy) of hydroxy aziridine trans-63 and TsNH2 (209 mg)
as a white solid and hydroxy aziridine cis-63 (418 mg, 53%) as a
colourless oil, RF(2 : 1 hexane–EtOAc) 0.1; IR (film) 3507 (OH),
2976, 2927, 1317 (SO2), 1155 (SO2), 1089, 998, 884, 687 cm-1; 1H
NMR (400 MHz, CDCl3) d 7.86 (d, J = 8.5, 2H, m-C6H4Me),
7.33 (d, J = 8.5, 2H, o-C6H4Me), 5.83 (ddt, J = 17.0, 10.0, 6.0,
=
=
1H, CH CH2), 5.07 (app. dq, J = 17.0, 1.5, 1H, CH CHAHB),
=
5.01 (app. dq, J = 10.0, 1.5, 1H, CH CHAHB), 4.24 (td, J =
8.0, 2.5, 1H, CHO), 3.42 (d, J = 2.5, 1H, CHN), 2.47–2.39 (m,
1H, CH), 2.46 (s, 3H, Me), 2.46–2.20 (m, 3H, 3 ¥ CH), 2.11
(dd, J = 14.0, 8.0, 1H, CH), 1.94 (dt, J = 13.0, 8.0, 1H, CH),
1.70 (ddd, J = 14.0, 10.5, 8.0, 1H, CH), 1.20 (ddt, J = 13.0,
10.5, 8.0, 1H, CH); 13C NMR (100.6 MHz, CDCl3) d 144.0 (ipso-
5-Allyl-6-[(4-methylphenyl)sulfonyl]-6-azabicyclo[3.1.0]hexan-
2-ol cis-62 and trans-62. Using the general procedure, allylic
alcohol 37 (80 mg, 0.6 mmol), chloramine-T trihydrate (200 mg,
0.7 mmol) and PhMe3NBr3 (24 mg, 0.1 mmol) in MeCN (3.5 mL)
gave the crude product, which contained a 65 : 35 mixture (by
1H NMR spectroscopy) of hydroxy aziridines cis-62 and trans-62.
Purification by flash chromatography on silica with hexane–Et2O
(3 : 7) as eluent gave hydroxy aziridine trans-62 (42 mg, 22%) as
a colourless oil, RF(3 : 7 hexane–Et2O) 0.22; IR (film) 3501 (OH),
2924, 1599, 1436, 1318 (SO2), 1154 (SO2), 1092, 990 cm-1; 1H NMR
(400 MHz, CDCl3) d 7.80 (d, J = 8.5, 2H, m-C6H4Me), 7.30 (d,
=
C6H4SO2), 137.9 (ipso-C6H4Me), 137.3 ( CH), 129.6 (m-C6H4Me),
127.1 (o-C6H4Me), 115.5 ( CH2), 72.9 (CHO), 61.1 (CN), 55.4
=
(CHN), 30.8 (CH2), 29.9 (CH2), 29.4 (CH2), 28.2 (CH2), 21.6
(Me); MS (CI, NH3) m/z 308 [(M + H)+, 70], 290 (20), 152
(100); HRMS (CI, NH3) m/z: [M + H]+ calcd for C16H21NO3S,
308.1320; found, 308.1312. Further purification of the mixture of
trans-63 and TsNH2 by partial recrystallisation from hexane–Et2O
followed by evaporation of the filtrate under reduced pressure gave
hydroxy aziridine trans-63 (118 mg, 15%) as a white solid, mp 80–
=
J = 8.5, 2H, o-C6H4Me), 5.93 (ddt, J = 17.0, 10.0, 7.0, 1H, CH),
◦
82 C, RF(2 : 1 hexane–EtOAc) 0.1; IR (Nujol mull) 3520 (OH),
=
5.23 (app. dq, J = 17.0, 1.5, 2H, CHAHB), 5.15 (ddt, J = 10.0,
1
1456, 1378, 1308 (SO2), 1152 (SO2), 1090, 1021 cm-1; H NMR
=
1.5, 1.0, 1H, CHAHB), 4.15 (d, J = 5.0, 1H, CHO), 3.35 (s, 1H,
(400 MHz, CDCl3) d 7.80 (d, J = 8.0, 2H, m-C6H4Me), 7.30 (d,
=
CHN), 3.07 (br dd, J = 15.0, 7.0, 1H, CHAHBCH CH2), 2.99
J = 8.0, 2H, o-C6H4Me), 5.90 (dddd, J = 17.0, 10.0, 6.5, 6.0, 1H,
=
(br dd, J = 15.0, 7.0, 1H, CHAHBCH CH2), 2.43 (s, 3H, Me),
=
=
CH CH2), 5.11 (app. dq, J = 17.0, 2.0, 1H, CH CHAHB), 5.04
1.99–1.88 (m, 2H, 2 ¥ CH), 1.68–1.58 (m, 1H, CH), 1.51 (ddd,
=
(ddt, J = 10.0, 2.0, 1.0, 1H, CH CHAHB), 4.12 (br t, J = 4.0,
J = 13.5, 7.0, 2.0, 1H, CH); 13C NMR (100.6 MHz, CDCl3) d
1H, CHO), 3.31 (s, 1H, CHN), 2.53–2.28 (m, 3H, 3 ¥ CH), 2.44
(s, 3H, Me), 2.01 (ddd, J = 13.5, 8.5, 1.5, 1H, CH), 1.93 (ddd,
J = 13.5, 10.5, 8.0, 1H, CH), 1.69–1.50 (m, 3H, 3 ¥ CH); 13C
NMR (100.6 MHz, CDCl3) d 143.8 (ipso-C6H4SO2), 138.1 (ipso-
=
143.9 (ipso-C6H4SO2), 137.9 (ipso-C6H4Me), 133.9 ( CH), 129.5
=
(m-C6H4Me), 127.1 (o-C6H4Me), 118.3 ( CH2), 72.6 (CHO), 61.3
(CN), 53.7 (CHN), 33.2 (CH2), 31.1 (CH2), 29.3 (CH2), 21.6 (Me);
MS (CI, NH3) m/z 311 [(M + NH4)+, 15], 294 (100), 276 (30),
138 (85); HRMS (CI, NH3) m/z: [M + H]+ calcd for C15H19NO3S,
294.1164; found, 294.1164 and hydroxy aziridine cis-62 (105 mg,
56%) as a colourless oil, RF(3 : 7 Et2O–hexane) 0.16; IR (film) 3502
(OH), 2955, 2928, 1598, 1437, 1399, 1318 (SO2), 1156 (SO2), 1091,
=
C6H4Me), 137.9 ( CH), 129.5 (m-C6H4Me), 127.1 (o-C6H4Me),
115.4 ( CH2), 72.6 (CHO), 62.1 (CN), 54.2 (CHN), 31.3 (CH2),
31.1 (CH2), 29.1 (CH2), 27.6 (CH2), 21.6 (Me); MS (CI, NH3)
m/z 325 [(M + NH4)+, 55], 308 (50), 189 (100), 119 (30); HRMS
(CI, NH3) m/z: [M + H]+ calcd for C16H21NO3S, 308.1320; found,
308.1326.
=
1
986 cm-1; H NMR (400 MHz, CDCl3) d 7.85 (d, J = 8.5, 2H,
m-C6H4Me), 7.31 (br d, J = 8.5, 2H, o-C6H4Me), 5.87 (ddt, J =
=
=
17.0, 10.0, 7.0, 1H, CH), 5.19–5.12 (m, 2H, CH2), 4.28 (br m,
7-(tert-Butylsulfonyl)-7-azabicyclo[4.1.0]heptan-2-ol
cis-64.
1H, CHO), 3.44 (d, J = 3.0, 1H, CHN), 2.96 (dd, J = 15.0, 7.0, 1H,
Using the general procedure, PhMe3NBr3 (150 mg, 0.4 mmol),
This journal is
The Royal Society of Chemistry 2008
Org. Biomol. Chem., 2008, 6, 4299–4314 | 4307
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