1371; NMR δH 0.95 (3H, d, J 7, CH(CH3)2), 0.98 (3H, d, J 7,
CH(CH3Ј)2), 1.33 (9H, s, C(CH3)3), 1.70–1.76 (1H, m,
CH(CH3)2), 2.74 (1H, dd, J 14, 6, C(1)H), 2.92 (1H, dd, J 14, 6,
C(1)HЈ), 3.74–3.80 (1H, m, C(2)H), 4.34–4.37 (1H, m, NH),
7.37 (2H, d, J 8.5, ArH), and 8.14 (2H, d, J 8.5, ArH); δC 17.41
(CH3), 19.57 (CH3), 28.42 (CH3), 31.42 (CH), 38.98 (CH2),
56.45 (CH), 79.29 (quat.), 123.49 (Ar), 130.03 (Ar), 146.59 (Ar),
147.02 (Ar), and 155.51 (CO); m/z (EI) (Mϩ Ϫ OC(CH3)3 235,
52%), 220 (22), 72 (84) and 57 (100).
C(2)H), 6.91 (1H, br d, J 8, NH), and 7.20–7.31 (5H, m, ArH);
δC (DMF-d7) 11.66 (CH2), 27.47 (CH3), 39.49 (CH2), 53.32
(CH), 77.60 (quat.), 125.99 (Ar), 127.98 (Ar), 128.87 (Ar),
138.25 (Ar), and 155.01 (CO).
(2S)-N-tert-Butoxycarbonyl-2-amino-3-phenyl-1-iodozincio-
propane 10. NMR δH (THF-d8) 0.33–0.49 (2H, m, C(1)H2), 1.37
(9H, s, C(CH3)3), 2.63 (1H, dd, J 6, 13, C(3)H), 2.82 (1H, dd,
J 7, 13, C(3)HЈ), 3.68–3.76 (1H, m, C(2)H), 6.50–6.54 (1H, br s,
NH), and 7.04–7.20 (5H, m, ArH); δC (THF-d8) 16.40 (CH2),
30.76 (CH3), 42.50 (CH2), 58.33 (CH), 82.73 (quat.), 117.58
(Ar), 128.33 (Ar), 131.67 (Ar), 140.05 (Ar), and 161.39 (CO).
NMR δH (DMF-d7) 0.32 (1H, dd, J 5.5, 13, C(1)H), 0.36 (1H,
dd, J 5.5, 13 (C(1)HЈ), 1.32 (9H, s, C(CH3)3), 2.74 (1H, dd, J 6,
13, C(3)H), 2.83 (1H, dd, J 6, 13, C(3)HЈ), 3.99–4.06 (1H, m,
C(2)H), 5.88 (1H, br d, J 8.5, NH), 7.10–7.25 (5H, m, ArH);
δC (DMF-d7) 15.72 (CH2), 27.28 (CH3), 44.38 (CH2), 52.88
(CH), 76.45 (quat.), 124.64 (Ar), 126.96 (Ar), 128.60 (Ar),
140.30 (Ar), and 154.62 (CO).
(2S)-N-tert-Butoxycarbonyl-3-methyl-1-(1-naphthyl)-2-
butylamine 8c. Treatment with iodonaphthalene (146 µL,
1.00 mmol) gave 8c (0.148 g, 63%), isolated as orange crystals.
Mp 100–101 ЊC (Found Mϩ 313.2046; C20H27NO2 requires
313.2042); [α]D 42.6 (c 0.580 in CHCl3 (Found: C, 75.61; H,
8.69; N, 4.46%: C20H27NO2 requires C, 76.64; H, 8.68; N,
4.47%); IR (KBr disc)/cmϪ1 3324, 2972, and 1681; NMR
δH 0.95–1.05 (6H, m, CH(CH3)2), 1.32 (9H, s, C(CH3)3), 1.77–
1.89 (1H, m, CH(CH3)2), 3.13–3.25 (2H, m, C(1)H2), 3.92–4.00
(1H, m, C(2)H), 4.40–4.45 (1H, m, NH), and 7.36–7.39 (1H, m,
ArH), 7.45–7.48 (1H, m, ArH), 7.52–7.55 (1H, m, ArH), 7.72
(1H, d, J 8 ArH), and 7.84 (1H, d, J 8, ArH); δC 16.88 (CH3),
19.78 (CH3), 28.32 (CH3), 30.63 (CH), 35.98 (CH2), 55.81 (CH),
78.85 (quat.), 123.85 (Ar), 125.28 (Ar), 125.47 (Ar), 126.06
(Ar), 126.20 (Ar), 127.05 (Ar), 128.71 (Ar), 128.71, 132.31 (Ar),
133.90 (Ar), 134.94 (Ar), and 155.68 (CO); m/z (EI) (Mϩ 313,
22%), 258 (47), 240 (45), 196 (26), 181 (29), 172 (35), 141 (59),
116 (70), 72 (100), and 57 (89).
Acknowledgements
We thank the EPSRC for a CASE studentship (C. H.), Smith-
Kline Beecham for support, and Dr H. Gardner, C. S. Dexter
and R. J. Outram for preliminary experiments. We also
thank Dr M. N. S. Hill, Mrs L. Cook, Mr D. Dunbar and
Mr S. Addison for obtaining spectroscopic and other data,
Miss G. Barr (Analytical Sciences Department, SmithKline
Beecham) for chiral phase HPLC analysis, and Mr E. Hart for
his invaluable technical assistance.
(2S)-N-tert-Butoxycarbonyl-3-methyl-1-(4-methoxyphenyl)-
2-butylamine 8d. Treatment with 1-iodo-4-methoxybenzene
(0.218 g, 1.00 mmol) gave 8d (0.116 g, 53%), isolated as a
white solid. Mp 104–105 ЊC (Found Mϩ 293.1990; C17H27NO3
requires 293.1991); [α]D25 13.6 (c 0.580 in CHCl3) (Found: C, 69.3;
H, 9.8; N, 4.6%: C17H27NO3 requires C, 69.6; H, 9.3; N, 4.8%);
IR (KBr disc)/cmϪ1 3389, 2979, 2837, and 1683; NMR δH 0.90
(3H, d, J 7, CH(CH3)2), 0.95 (3H, d, J 7, CH(CH3Ј)2), 1.38 (9H,
s, C(CH3)3), 1.67–1.75 (1H, m, CH(CH3)2), 2.62 (1H, dd, J 15,
5, C(1)H), 2.71 (1H, dd, J 15, 5, C(1)HЈ), 3.64–3.72 (1H, m,
C(2)H), 3.78 (3H, s), 4.26–4.35 (1H, m, NH), 6.82 (2H, d, J 8.5,
ArH), and 7.10 (2H, d, J 8.5, ArH); δC 17.22 (CH3), 19.72
(CH3), 28.38 (CH3), 30.51 (CH), 37.75 (CH2), 55.25 (CH), 78.86
(quat.), 113.74 (Ar), 130.14 (Ar), 130.78 (Ar), 155.74 (Ar), and
158.04 (CO); m/z (EI) (Mϩ 293, 19%), 220 (54), 194 (19), 172
(30), 161 (6), 150 (7), 121 (85), 72 (100), and 57 (90).
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(2S)-N-tert-Butoxycarbonyl-2-amino-3-phenyl-1-iodopropane 13
NMR δH (THF-d8) 1.43 (9H, s, C(CH3)3), 2.90 (2H, d, J 7,
C(3)H2), 3.26 (1H, dd, J 5, 12, C(1)H), 3.52 (1H, dd, J 5, 12,
C(1)HЈ), 3.63–3.71 (1H, m, C(2)H), 6.28 (1H, br d, J 7, NH),
and 7.22–7.31 (5H, m, ArH); δC (THF-d8) 14.62 (CH2), 30.04
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C(3)H), 2.94 (1H, dd, J 8, 14, C(3)HЈ), 3.33 (1H, dd, J 7, 10,
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Paper a907629h
J. Chem. Soc., Perkin Trans. 1, 2000, 219–223
223