SN 2-type ring opening of substituted-N-tosylaziridines with zinc (II) halides
953
other diastereomer of 2d (X = Cl): 1H NMR (400 MHz, 2.2g trans-2-Chloro-N-tosylcyclohexanamine (2g):5a,6
CDCl3) δ 0.02 (s, 6H), 0.88 (s, 9H), 2.39 (s, 3H, CH3), The general method 1 was followed, when 1c reacted
3.46 (dd, J = 10.3, 4.4 Hz, 1H), 3.74–3.81 (m, 1H), with ZnCl2 to afford 2g as white solid in 82% yield;
4.02 (dd, J = 10.3, 2.7 Hz, 1H), 4.82 (d, J = 9.5 Hz, 1H NMR (400 MHz, CDCl3) δ 1.15–1.29 (m, 3H),
1H, NH), 4.95 (d, J = 7.8 Hz, 1H), 7.12–7.26 (m, 7H, 1.49–1.65 (m, 3H), 2.08–2.21 (m, 2H), 2.36 (s, 3H),
Ar–H), 7.5 (d, J = 8.3 Hz, 2H); 13C NMR (100 MHz, 2.98–3.04 (m, 1H), 3.60–3.66 (m, 1H), 4.86 (d, J =
CDCl3) δ −5.5, 18.2, 21.4, 25.7, 60.1, 60.9, 61.7, 5.4 Hz, 1H, NH); 7.24 (d, J = 8.5 Hz, 2H), 7.68–7.72
126.9, 127.3, 128.1, 128.4, 129.5, 137.2, 137.6, 143.2; (m, 2H). 13C NMR (100 MHz, CDCl3) 21.6, 23.4, 24.5,
FAB Mass: m/z 455 M++2, 454 M++1, 438, 418, 396, 32.6, 35.0, 58.8, 62.2, 127.3, 129.6, 136.9, 143.5; FAB
388, 341, 328, 286, 263, 228, 184, 155, 118, 91. HRMS Mass: m/z 288 (M++1).
(ES+) for (M++1) C22H32ClNO3SSi, calcd 454.1639;
found 454.1638.
2.2h trans-2-Bromo-N-tosylcyclohexanamine (2h):5a
The general method 1 was followed, when 1c reacted
2.2e Spectral data of 2e:5a The general method 1 was
followed, when 1b reacted with ZnBr2 to afford 2e as
colourless liquid in 52% combined yield; It was iso-
lated as an inseparable mixture of two diastereomers;
with ZnBr2 to afford 2h as white solid in 78% yield;
1H NMR (400 MHz, CDCl3) δ 1.17–1.28 (m, 3H),
1.58–1.76 (m, 3H), 2.20–2.23 (m, 2H), 2.36 (s, 3H),
3.07–3.11 (m, 1H), 3.74–3.80 (m, 1H), 4.88 (d, J =
5.1 Hz, 1H, NH), 7.24 (d, J = 8.0 Hz, 2 H), 7.70 (dd,
J = 8.2, 1.7 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
21.5, 23.4, 25.4, 35.8, 55.1, 58.7, 127.3, 129.6, 136.9,
143.5; FAB Mass: m/z 332 (M++1).
1
For the major diastereomer of 2e (X = Br): H NMR
(400 MHz, CDCl3) δ −0.01 (s, 3H), 0.00 (s, 3H), 0.88
(s, 9H), 2.41 (s, 3H), 3.48 (dd, J = 10.0, 3.8 Hz, 1H),
3.54 (dd, J = 7.08, 4.12 Hz, 1H), 3.62–3.67 (m, 1H),
4.99 (d, J = 7.8 Hz, 1H), 5.25 (d, J = 5.6 Hz, 1H),
7.17–7.29 (m, 7H), 7.63 (d, J = 8.3 Hz, 2H); 13C NMR
(100 MHz, CDCl3) δ −5.5. 18.1, 21.4, 25.7, 55.2, 60.6,
62.9, 126.9, 128.0, 128.4, 129.5, 137.4, 138.3, 143.3;
2.2i trans-2-Iodo-N-tosylcyclohexanamine (2i):5a The
general method 1 was followed, when 1c reacted
with ZnI2 to afford 2i as white solid in 86% yield;
1H NMR (400 MHz, CDCl3) δ 1.18–1.34 (m, 3H),
1.44–1.59 (m, 2H), 1.84–1.97 (m, 1H), 2.15–2.30 (m,
2H), 2.36 (s, 3H), 3.16–3.19 (m, 1H), 3.90–3.92 (m,
1H), 4.92 (d, J = 5.6 Hz, 1H), 7.24 (d, J = 8.1 Hz, 2H),
7.72 (d, J = 8.3 Hz, 2H); 13C NMR (100 MHz, CDCl3)
21.5, 23.6, 26.7, 33.1, 34.9, 37.9, 59.2, 127.4, 129.6,
137.1, 143.5; FAB Mass: m/z 380 (M++1).
1
for the other diastereomer of 2e (X = Br): H NMR
(400 MHz, CDCl3) δ 0.05 (s, 3H), 0.08 (s, 3H), 0.91
(s, 9H), 2.42 (s, 3H), 3.56–3.57 (m, 1H), 3.91–3.93
(m, 1H), 4.15 (dd, J = 9.7, 2.2 Hz, 1H), 4.85
(d, J = 9.5 Hz, 1H), 5.02 (d, J = 8.3 Hz, 1H), 7.17–
7.29 (m, 7H), 7.51 (d, J = 8.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3) δ −5.6, 18.2, 21.4, 25.8, 52.5,
59.8, 62.5, 127.0, 128.3, 128.4, 129.5, 137.3, 138.2,
143.3. HRMS (ES+) for (M–Br)+ C22H32BrNO3SSi,
calcd 418.1872; found 418.1870.
2.2j 2-Chloro-3-phenyl-N-tosylpropan-1-amine(2j):5a,6
The general method 1 was followed, when 1d reacted
with ZnCl2 to afford a mixture of 2j and 3j (28:72) as
white solid in 87% combined yield; For regioisomer 2j:
1H NMR (400 MHz, CDCl3) δ 2.36 (s, 3H), 2.88–3.07
(m, 3H), 3.20–3.26 (m, 1H), 3.98–4.05 (m, 1H), 4.87
(t, J = 6.8 Hz, 1H, NH), 7.05–7.07 (m, 2H), 7.16–7.24
(m, 5H), 7.62 (d, J = 8.1 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 21.5, 41.7, 48.3, 61.7, 127.0, 127.2, 128.6,
129.2, 129.8, 136.3, 136.6, 143.7.
2.2f Spectral data of 2f:5a The general method 1 was
followed, when 1b reacted with ZnI2 to afford 2f as
colourless liquid in 56% yield as a single regioiso-
mer. It was isolated as an inseparable mixture of two
diastereomers. For the major diastereomer of 2f (X = I):
1H NMR (400 MHz, CDCl3) δ −0.04 (d, J = 1.4 Hz,
3H), −0.01 (d, J = 1.4 Hz, 3H), 0.82 (d, J =
1.7 Hz, 9H), 2.33 (s, 3H), 3.54–3.58 (m, 1H), 3.78–3.83
(m, 1H), 4.08–4.12 (m, 1H), 4.71 (d, J = 9.0 Hz, 1H),
5.09 (d, J = 9.0 Hz, 1H), 7.06–7.21 (m, 7H), 7.42 (dd,
J = 8.3, 1.4 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
−5.6. 18.2, 21.4, 25.8, 31.5, 60.3, 63.8, 127.0, 127.9,
128.4, 128.5, 129.5, 137.3, 140.2, 143.3. HRMS (ES+)
for (M++1) C22H32INO3SSi, calcd 546.0995; found
546.0997.
2.2k 1-Chloro-3-phenyl-N-tosylpropan-2-amine(3j):5a
1H NMR (400 MHz, CDCl3) δ 2.41 (s, 3H), 2.76 (dd,
J = 13.7, 6.4 Hz, 1H), 2.87 (dd, J = 13.6, 7.8 Hz,
1H), 3.41–3.50 (m, 2H), 3.65–3.73 (m, 1H), 4.89 (d,
J = 8.0 Hz, 1H, NH), 7.03–7.07 (m, 2H), 7.15–7.26 (m,
5H), 7.64 (d, J = 8.3 Hz, 2H); 13C NMR (100 MHz,