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1
4.2.1.4. 3-Methyl-4-nonynyl-1-amine (13). H NMR (CDCl3,
500 MHz) d 2.83e2.76 (m, CH2NH2), 2.49e2.45 (m, 1H,
CHC^C), 2.15 (td, J¼6.87, 2.07 Hz, 2H, C^CCH2), 1.53e
1.46 (m, 4H, NH2CH2CH2, NH2), 1.45e1.33 (m, 4H, C^
CCH2CH2CH2), 1.15 (d, J¼6.89 Hz, 3H, CHCH3), 0.90 (t,
J¼7.11 Hz, 3H, CH2CH3). 13C NMR (CDCl3, 125 MHz) d 84.1,
80.8, 41.2, 40.4, 31.3, 23.6, 21.9, 21.7, 18.4, 13.6. IR (film) 3353,
2958, 2934, 2859, 2158, 1488, 1382 cmꢁ1. HRMS(EI):calcdfor
C10H19N (Mþ), 153.1517; found, 153.1515.
4.2.1.9. 2-Methyl-5-pentyl-3,4-dihydro-2H-pyrrole (17). 1H
NMR (CDCl3, 500 MHz) d 4.04e3.99 (m, 1H, CHN), 2.57e
2.50 (m, 1H, CH2C]N), 2.45e2.40 (m, 1H, CH2C]N), 2.30
(t, J¼7.75 Hz, N]CCH2), 2.10e2.03 (m, 1H, NCHCH2),
1,60e1.54 (m, 2H, CCH2CH2CH2), 1.39e1.28 (m, 5H,
CCH2CH2CH2CH2, NCHCH2), 1.27 (d, J¼7.0 Hz, 3H,
CHCH3), 0.89 (t, J¼7.0 Hz, 3H, CH2CH3). 13C NMR (CDCl3,
125 MHz) d 177.4, 67.8, 37.5, 34.1, 31.9, 30.9, 26.5, 22.7,
22.3, 14.2. IR (film) 2950, 2920, 2860, 1620, 1425, 1410,
1360 cmꢁ1. HRMS (EI): calcd for C10H19N (Mþ), 153.1517;
found, 153.1516.
4.2.1.5. 3-Benzyloxy-2,2-dimethyl-5-trimethylsilyl-4-pentynyl-
1-amine (14). H NMR (CDCl3, 500 MHz) d 7.35 (d, J¼
1
4.5 Hz, 4H, Ph), 7.31e7.28 (m, 1H, Ph), 4.83 (d, J¼12.0 Hz,
1H, CH2Ph), 4.47 (d, J¼12.0 Hz, 1H, CH2Ph), 3.87 (s, 1H,
CHOCH2), 2.89 (d, J¼13.0 Hz, 1H, CHHNH2), 2.67 (d, J¼
13.0 Hz, 1H, CHHNH2), 1.63 (br, 1H, NH2), 1.03 (s, 3H,
(CH3)2C), 1.01 (s, 3H, (CH3)2C), 0.21 (s, 9H, Si(CH3)3). 13C
NMR (CDCl3, 125 MHz) d 138.3, 128.5, 128.2, 127.8, 103.4,
92.5, 75.6, 71.0, 50.1, 39.6, 22.2, 21.5, 0.2. IR (film) 3396,
3064, 2957, 2887, 2167, 1652, 1608, 1496, 1454, 1386, 1249,
1069, 840, 759, 697 cmꢁ1. HRMS (EI): calcd for C17H27NOSi
(Mþ), 289.1862; found, 289.1864.
4.2.1.10. 4-Methyl-5-pentyl-3,4-dihydro-2H-pyrrole (18). 1H
NMR (CDCl3, 400 MHz) d 3.82e3.76 (m, 1H, CH2N), 3.66e
3.59 (m, 1H, CH2N), 2.78e2.68 (m, 1H, CHC]N), 2.35e
2.18 (m, 2H, N]CCH2), 2.15e2.07 (m, 1H, NCH2CH2),
1.67e1.56 (m, 2H, NCHCH2), 1.48e1.41 (m, 1H, NCH2CH2),
1.32 (br m, 2H, CCH2CH2CH2CH2), 1.22 (td, J¼5.02, 1.09 Hz,
2H, CCH2CH2CH2CH2), 1.17 (td, J¼5.58, 1.03 Hz, 2H,
CCH2CH2CH2CH2), 1.11 (dd, J¼7.13, 1.34 Hz, 3H, CHCH3),
0.89 (t, J¼6.10 Hz, 3H, CH2CH3). 13C NMR (CDCl3,
100 MHz) d 182.3, 58.8, 44.4, 32.2, 32.1, 31.69, 26.3, 22.9,
17.8, 14.4. IR (film) 2950, 2928, 2860, 1622 cmꢁ1. HRMS
(EI): calcd for C10H19N (Mþ), 153.1517; found, 153.1515.
4.2.1.6. 4-Methyl-5-decynyl-1-amine (15). 1H NMR (CDCl3,
500 MHz) d 2.67e2.60 (m, 2H, CH2NH2), 2.34e2.31
(m, 1H, C^CCHCH3), 2.09 (td, J¼6.5, 2.0 Hz, 2H,
CHC^CCH2), 1.57e1.48 (m, 1H, CH2CHCH3), 1.48e1.46
(m, 1H, CH2CHCH3), 1.44e1.29 (m, 6H, NH2CH2CH2,
C^CCH2CH2CH2), 1.24 (br, 1H, NH2), 1.08 (d, J¼7.0 Hz,
CH3CHC^C), 0.84 (t, J¼7.0 Hz, 3H, CH2CH2CH3). 13C
NMR (CDCl3, 125 MHz) d 84.6, 80.6, 42.2, 34.7, 31.8,
31.4, 26.0, 22.0, 21.7, 18.5, 13.7. IR (film) 3366, 3296, 2933,
4.2.1.11. 4-Benzyloxy-3,3,5-trimethyl-3,4-dihydro-2H-pyrrole
1
(20). H NMR (CDCl3, 500 MHz) d 7.38 (d, 2H, J¼4.0 Hz,
Ph), 7.34e7.31 (m, 1H, Ph), 4.75 (d, J¼12.0 Hz, 1H, CH2Ph),
4.60 (d, J¼12.0 Hz, 1H, CH2Ph), 3.98 (s, 1H, CHOBn), 3.55
(d, J¼14.5 Hz, 1H, CH2N), 3.37 (d, J¼14.5 Hz, 1H, CH2N), 2.03
(s, 3H, CCH3), 1.17 (s, 3H, C(CH3)2), 1.03 (s, 3H, C(CH3)2). 13
C
NMR (CDCl3, 125 MHz) d 176.2, 138.3, 128.7, 128.1, 128.1,
92.8, 73.8, 71.9, 42.8, 26.7, 21.6, 18.0. IR (film) 3334, 2981,
2361, 1626, 1481, 1377, 1309, 754, 730 cmꢁ1. HRMS (CI): calcd
for C14H20NO (Mþ1), 218.1544; found, 218.1534.
2862, 2152, 1608, 1587, 1455, 1388, 1095, 845, 784 cmꢁ1
HRMS (EI): calcd for C11H21N (Mþ), 167.1674; found,
167.1675.
.
1
1
4.2.1.7. 2,2-Dimethyl-7-phenyl-6-heptynyl-1-amine (16). H
4.2.1.12. 5-Methyl-6-pentyl-2,3,4,5-tetrahydropyridine (21). H
NMR (CDCl3, 500 MHz) d 7.41 (dd, J¼7.75, 2.0 Hz, 2H, Ph),
7.30e7.25 (m, 3H, Ph), 2.46 (s, 2H, CH2NH2), 2.39 (t, J¼
7.0 Hz, 2H, CH2^C), 1.59e1.53 (m, 2H, CH2CH2), 1.37e1.33
(m, 2H, CH2CH2), 1.18 (br, 2H, NH2), 0.87 (s, 6H, (CH3)2C).
13C NMR (CDCl3, 125 MHz) d 131.5, 128.1, 127.4, 124.0,
90.2, 80.7, 52.7, 38.7, 34.3, 24.7, 23.6, 20.2. IR (film) 3346,
3067, 2936, 2864, 2232, 1560, 1542, 1490, 756 cmꢁ1. HRMS
(EI): calcd for C15H21N (Mþ), 215.1674; found, 215.1671.
NMR (CDCl3, 500 MHz) d 3.58e3.50 (m, 2H, CH2N), 2.26e
2.16 (m, 3H, CH2C]N, N]CCHCH3), 1.80e1.74 (m, 1H,
CH2CHC]N), 1.66e1.59 (m, 1H, CH2CHeC]N), 1.56e
1.46 (m, 3H, CH2CH2C]N, NCH2CH2), 1.45e1.40 (m, 1H,
NCH2CH2), 1.35e1.25 (m, 4H, CH2CH2CH3), 1.13 (d, J¼
7.5 Hz, CHCH3), 0.89 (t, J¼7.0 Hz, 3H, CH2CH3). 13C NMR
(CDCl3, 125 MHz) d 49.6, 38.4, 32.9, 32.0, 28.3, 26.6, 22.7,
20.0, 18.8, 14.1. IR (film) 2955, 2930, 2864, 1663 cmꢁ1
.
HRMS (EI): calcd for C11H21N (Mþ), 167.1674; found,
167.1676.
4.2.1.8. 6-Pentyl-2,3,4,5-tetrahydropyridine (4). Subjecting
5-decynyl-1-amine (61.3 mg, 0.4 mmol) to 5 mol % 5 under the
general procedure provided the cyclic imine 4 (58.2 mg, 95%).
1H NMR (CDCl3, 500 MHz) d 3.48 (t, J¼6.5 Hz, 2H, CH2N),
2.08e2.03 (m, 4H, CH2C]N, N]CCH2), 1.62e1.57 (m, 2H,
CH2CH2C]N), 1.51e1.43 (m, 4H, CH2CH2N, CCH2CH2),
1.28e1.21 (m, 4H, CH2CH2CH3), 0.87 (t, J¼6.75 Hz, 3H,
CH2CH3). 13C NMR (CDCl3, 125 MHz)d 171.3, 49.2, 41.2, 31.8,
29.1, 26.3, 22.6, 22.0, 19.7, 14.1. IR (film) 2958, 2934, 2860,
1660 cmꢁ1. HRMS (EI): calcd for C10H19N (Mþ), 153.1517;
found, 153.1519.
4.2.1.13. 7-Benzyl-3,3-dimethyl-3,4,5,6-tetrahydro-2H-azepine
1
(22). H NMR (CDCl3, 500 MHz) d 7.30e7.25 (m, 4H, Ph),
7.22e7.20 (m, 1H, Ph), 3.55 (s, 2H, CH2Ph), 3.40 (s, 2H,
CH2N), 2.24 (t, J¼5.75 Hz, 2H, CH2C]N), 1.40 (t, J¼6.0 Hz,
2H, (CH3)2CCH2), 1.20e1.14 (m, 2H, CH2CH2CH2), 0.88 (s,
6H, (CH3)2C). 13C NMR (CDCl3, 125 MHz) d 176.8, 137.1,
129.4, 128.6, 126.9, 61.9, 49.7, 44.4, 32.1, 27.3, 19.5, 16.3. IR
(film) 3100e2860, 1680, 1485 cmꢁ1. HRMS (EI): calcd for
C15H21N (Mþ), 215.1674; found, 215.1668.