586
Y. Hari, T. Aoyama
PAPER
1H NMR (CDCl3): d = 1.23 (3 H, s), 1.24 (3 H, s), 1.38–1.48 (1 H,
m), 1.58–2.14 (15 H, m), 2.21–2.37 (2 H, m), 2.43–2.53 (1 H, m),
3.87 (1 H, br), 4.78 (1 H, br).
13C NMR (CDCl3): d = 19.8, 19.9, 21.3, 21.5, 27.3, 27.7, 29.4, 29.9,
30.5, 30.8, 43.3, 43.7, 43.8, 49.0, 50.7, 67.7, 166.1, 212.3.
1H NMR (CDCl3): d = 0.81 (3 H, s), 1.01–1.08 (1 H, m), 1.14 (3 H,
s), 1.27–1.36 (1 H, m), 1.44–1.55 (1 H, m), 1.63–1.84 (8 H, m),
2.14, 3.11 (2 H, AB, J = 13 Hz), 2.48–2.51 (2 H, m), 2.63–2.66 (2
H, m), 3.94 (1 H, dd, J = 4, 8 Hz), 5.06 (1 H, br).
13C NMR (CDCl3): d = 20.4, 20.6, 23.9, 27.5, 33.4, 38.9, 44.9, 47.5,
51.2, 55.8, 55.9, 78.4.
MS (EI): m/z (%) = 223 (M+, 71.4), 41 (100).
HRMS (EI): m/z calcd for C14H25NO (M+): 223.1936; found:
MS (EI): m/z (%) = 289 (M+, 59.5), 165 (100).
Anal. Calcd for C18H27NO2: C, 74.70; H, 9.40; N, 4.84. Found: C,
74.42; H, 9.34; N, 5.08.
223.1907.
g-Amino Alcohol 1; (1R,2R)-10-(Dimethylamino)isoborneol
(1a); Typical Procedure
(1R,2R)-10-Piperidinoisoborneol (1e)
LiAlH4 (109 mg, 2.87 mmol) was added to a solution of 3a (300 mg,
1.43 mmol) in THF (6 ml) at 0 °C under argon. The mixture was
stirred for 0.5 h at r.t. and then refluxed for 2 h. After adding
Na2SO4·10H2O at 0 °C, the mixture was filtered. The filtrate was
concentrated in vacuo and the residue was purified by flash column
chromatography (EtOAc–MeOH, 1:1) to give 1a (260 mg, 92%);
colorless oil; [a]D25 –75.3 (c = 0.61, CHCl3).
Yield: 96%; colorless oil; [a]D26 –68.0 (c = 1.12, CHCl3).
IR (neat): 3383, 2934, 2878, 2806 cm–1.
1H NMR (CDCl3): d = 0.80 (3 H, s), 0.97–1.07 (1 H, m), 1.15 (3 H,
s), 1.25–1.71 (11 H, m), 1.77–1.85 (1 H, m), 2.25, 2.70 (2 H, AB,
J = 13 Hz), 2.35 (2 H, br), 2.57 (2 H, br), 3.96 (1 H, dd, J = 4, 8 Hz),
5.78 (1 H, br).
13C NMR (CDCl3): d = 20.5, 24.0, 26.3, 27.8, 34.4, 39.2, 44.8, 47.9,
50.7, 56.1, 59.5, 78.4.
MS (EI): m/z (%) = 237 (M+, 44.8), 84 (100).
HRMS (EI): m/z calcd for C15H27NO (M+): 237.2093; found:
IR (neat): 3416, 2951, 2878, 1454 cm–1.
1H NMR (CDCl3): d = 0.79 (3 H, s), 0.99–1.09 (1 H, m), 1.14 (3 H,
s), 1.30–1.40 (1 H, m), 1.45–1.56 (1 H, m), 1.64–1.86 (4 H, m),
2.11, 2.79 (2 H, AB, J = 13 Hz), 2.28 (6 H, s), 3.98 (1 H, dd, J = 4,
8 Hz), 5.15 (1 H, br).
MS (EI): m/z = 197 (M+, 14.0), 45 (100).
HRMS (EI): m/z calcd for C12H23NO (M+): 197.1780; found:
237.2087.
(1R,2R)-10-(Hexamethyleneimino)isoborneol (1f)
Yield: 97%; colorless amorphous solid; mp <30 °C; [a]D –44.4
(c = 1.09, CHCl3).
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197.1795.
IR (neat): 3317, 2924, 1475, 1360 cm–1.
(1R,2R)-10-(Diisobutylamino)isoborneol (1b)
Yield: 93%; colorless oil; [a]D25 –147.6 (c = 0.88, CHCl3).
1H NMR (CDCl3): d = 0.79 (3 H, s), 0.98–1.08 (1 H, m), 1.15 (3 H,
s), 1.29–1.38 (1 H, m), 1.44–1.74 (12 H, m), 1.78–1.87 (1 H, m),
2.54, 2.73 (2 H, AB, J = 13 Hz), 2.57–2.64 (2 H, m), 2.68–2.75 (2
H, m), 3.95 (1 H, dd, J = 4, 8 Hz), 5.86 (1 H, br).
13C NMR (CDCl3): d = 20.5, 26.9, 27.7, 28.4, 34.1, 39.1, 44.7, 47.9,
51.0, 57.2, 59.2, 78.6.
IR (neat): 3383, 2953, 2804, 1468 cm–1.
1H NMR (CDCl3): d = 0.80 (3 H, s), 0.87 (6 H, d, J = 7 Hz), 0.98 (6
H, d, J = 7 Hz), 1.01–1.09 (1 H, m), 1.15 (3 H, s), 1.32–1.42 (1 H,
m), 1.47–1.57 (1 H, m), 1.64–1.87 (6 H, m), 1.94 (2 H, dd, J = 3, 13
Hz), 2.09, 2.89 (2 H, AB, J = 13 Hz), 2.30 (2 H, dd, J = 10, 13 Hz),
3.95 (1 H, dd, J = 4, 8 Hz), 5.38 (1 H, s).
MS (EI): m/z = 251 (M+, 64.2), 70 (100).
13C NMR (CDCl3): d = 20.5, 20.6, 21.0, 21.7, 26.3, 27.9, 34.8, 39.0,
Anal. Calcd for C16H29NO: C, 76.44; H, 11.63; N, 5.57. Found: C,
76.22; H, 11.68; N, 5.50.
44.6, 48.5, 50.7, 56.9, 65.4, 77.6.
MS (EI): m/z 281 (M+, 5.7), 86 (100).
(1R,2R)-10-(Heptamethyleneimino)isoborneol (1g)
Anal. Calcd for C18H35NO: C, 76.81; H, 12.53; N, 4.98. Found: C,
76.58; H, 12.65; N, 4.94.
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Yield: 93%; white powder; mp 36–38 °C; [a]D –48.4 (c = 1.04,
CHCl3).
IR (Nujol): 3420 cm–1.
(1R,2R)-10-(Diisopropylamino)isoborneol (1c)6
Yield: 95%; white powder; mp 69–71 °C; [a]D –68.6 (c = 1.48,
CHCl3).
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1H NMR (CDCl3): d = 0.79 (3 H, s), 1.00–1.09 (1 H, m), 1.14 (3 H,
s), 1.31–1.40 (1 H, m), 1.45–1.75 (14 H, m), 1.78–1.85 (1 H, m),
2.41, 2.74 (2 H, AB, J = 13 Hz), 2.48–2.69 (4 H, m), 3.98 (1 H, dd,
J = 4, 8 Hz), 5.06 (1 H, br).
13C NMR (CDCl3): d = 20.5, 20.6, 25.6, 27.5, 27.7, 33.4, 38.8, 44.7,
48.0, 51.3, 56.8, 60.2, 78.2.
IR (neat): 3344 cm–1.
1H NMR (CDCl3): d = 0.84 (3 H, s), 0.99 (6 H, d, J = 7 Hz), 1.00–
1.08 (1 H, m), 1.09 (6 H, d, J = 7 Hz), 1.19 (3 H, s), 1.29–1.37 (1 H,
m), 1.47–1.57 (1 H, m), 1.64–1.83 (4 H, m), 2.56, 2.78 (2 H, AB,
J = 14 Hz), 3.14 (2 H, sept, J = 7 Hz), 3.93 (1 H, dd, J = 4, 8 Hz),
6.01 (1 H, br).
13C NMR (CDCl3): d = 17.3, 20.5, 20.7, 22.5, 27.9, 35.0, 39.3, 44.0,
44.5, 47.9, 48.6, 50.0, 78.1.
MS (EI): m/z 265 (M+, 27.1), 126 (100).
Anal. Calcd for C17H31NO: C, 76.92; H, 11.77; N, 5.28. Found: C,
76.65; H, 11.80; N, 5.11.
MS (EI): m/z 253 (M+, 8.0), 238 (100).
HRMS (EI): m/z calcd for C16H31NO (M+): 253.2406; found:
(1R,2R)-10-Morpholinoisoborneol (1h)
Yield: 99%; white powder; mp 42–43 °C; [a]D –75.8 (c = 1.04,
CHCl3).
IR (neat): 3404, 2922, 1454, 1377 cm–1.
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253.2408.
1H NMR (CDCl3): d = 0.81 (3 H, s), 1.00–1.09 (1 H, m), 1.14 (3 H,
s), 1.24–1.34 (1 H, m), 1.49–1.60 (1 H, m), 1.65–1.87 (4 H, m),
2.29, 2.75 (2 H, AB, J = 13 Hz), 2.39–2.47 (2 H, m), 2.63–2.67 (2
H, m), 3.71 (4 H, dd, J = 5, 5 Hz), 3.95 (1 H, dd, J = 4, 8 Hz), 4.78
(1 H, br).
(1R,2R)-10-Pyrrolidinoisoborneol (1d)
Yield: 92%; colorless oil; [a]D25 –75.7 (c = 1.18, CHCl3).
IR (neat): 3416, 2953, 2878, 2800 cm–1.
Synthesis 2005, No. 4, 583–587 © Thieme Stuttgart · New York