C. Kobler et al. / Tetrahedron 60 (2004) 10397–10410
10405
Table 10. Spectroscopic data of the 2- and 3-substituted cyclohexanone cyanohydrins 2, 5, and 7
Compound
1H NMR (250 MHz) (J in Hz) d
13C NMR (125.8 MHz) d
rac-2a
1.12 (d, 3JZ6.8, 0.7H, cis-CH3), 1.15 (d, 3JZ6.6, 2.3H, trans-CH3),
1.22–1.45 (m, 2H, 2CH), 1.52–1.91 (m, 6H, 6CH), 2.09–2.25 (m, 1H,
C6Heq), 2.55, 2.93 (br s, 1H, OH)
16.01 (cis-CH3), 16.10 (trans-CH3), 19.97 (cis-C5H2), 23.62 (trans-
C5H2), 24.28 (cis-C4H2), 24.80 (trans-C4H2), 28.21 (cis-C3H2), 31.68
(trans-C3H2), 37.05 (cis-C6H2), 38.62 (trans-C6H2), 39.19 (cis-C2H),
41.65 (trans-C2H), 70.77 (cis-C1), 74.84 (trans-C1), 120.21 (trans-
CN), 122.51 (cis-CN)
3
3
rac-2b
rac-2c
0.97 (t, JZ7.4, 2.3H, trans-CH2CH3), 0.98 (t, JZ7.3, 0.7H, cis-
CH2CH3), 1.11–1.44 (m, 4H, 4CH), 1.53–2.02 (m, 6H, 6CH), 2.08–2.
24 (m, 1H, C6Heq), 2.62 and 3.03 (br s, 1H, OH)
11.59 (trans-CH2CH3), 11.86 (cis-CH2CH3), 20.24 (cis-C5H2), 22.85
(trans-C5H2), 23.29 (cis-CH2CH3), 23.44 (trans-CH2CH3), 24.18, 24.
66, 24.71, 27.81 (C4H2), (C3H2), 37.49 (cis-C6H2), 39.08 (trans-
C6H2), 45.99 (cis-C2H), 48.33 (trans-C2H), 71.40 (cis-C1), 74.20
(trans-C1), 120.50 (trans-CN), 122.66 (cis-CN)
14.12 (cis-CH2CH2CH3), 14.20 (trans-CH2CH2CH3), 20.19 (CH2-
CH2CH3), 20.35 (cis-C5H2), 23.41 (trans-C5H2), 24.22 (cis-C4H2),
24.73 (trans-C4H2), 25.29 (cis-C3H2), 28.42 (trans-C3H2), 32.24
(trans-CH2CH2CH3), 32.59 (cis-CH2CH2CH3), 37.49 (cis-C6H2), 39.
04 (trans-C6H2), 43.97 (cis-C2H), 46.41 (trans-C2H), 71.44 (cis-C1),
74.20 (trans-C1), 120.52 (trans-CN), 122.64 (cis-CN)
3
3
0.94 (t, JZ7.1, 2.3H, trans-CH2CH3), 0.95 (t, JZ7.0, 0.7H, cis-
CH2CH2CH3), 1.12–1.36 (m, 4H, 1CH, CH2CH2CH3, CHAHCH2-
CH3), 1.41–1.98 (m, 8H, 7CH, CHHBCH2CH3), 2.09–2.27 (m, 1H,
1C6Heq), 2.55 and 2.95 (br s, 1H, OH)
rac-2d
rac-2e
0.97–1.04 (m, 6H, CH(CH3)2), 1.18–1.90 (m, 8H, 8CH), 2.02 (br s, 0.
3H, OH), 2.09–2.26 (m, 2H, C6Heq, 1CH), 2.47 (br s, 0.7H, OH)
17.45, 18.67, 23.23, 23.32 (CH(CH3)2)*), 20.13, 20.26, 23.65, 23.90,
25.28, 25.33 (C5H2), (C4H2), (C3H2), 26.29, 29.71 (CH(CH3)2), 39.
71 (cis-C6H2), 41.07 (trans-C6H2), 49.42 (cis-C2H), 52.36 (trans-
C2H), 71.20 (cis-C1), 72.53 (trans-C1), 121.23 (trans-CN), 121.69
(cis-CN)*) rotamers
1.11–1.40 (m, 2H, 2CH), 1.53–1.92 (m, 6H, 6CH), 2.03–2.36 (m, 2H,
2CH), 2.47–2.73 (m, 1H, 1CH), 3.19 (br s, 1H, OH), 5.06–5.28 (m,
2H, CH2CH]CH2), 5.74–5.97 (m, 1H, CH2CH]CH2)
20.15 (cis-C5H2), 23.29 (trans-C5H2), 24.23 (cis-C4H2), 24.75 (trans-
C4H2), 25.03 (cis-C3H2), 29.20 (trans-C3H2), 35.36 (cis-CH2CH]
CH2), 36.19 (trans-CH2CH]CH2), 37.59 (cis-C6H2), 38.80 (trans-
C6H2), 43.97 (cis-C2H), 46.38 (trans-C2H), 71.17 (cis-C1), 74.68
(trans-C1), 117.62 (cis-CH2CH]CH2), 117.79 (trans-CH2CH]
CH2), 120.21 (trans-CN), 122.35 (cis-CN), 136.00 (cis-CH2CH]
CH2), 136.86 (trans-CH2CH]CH2)
14.00 (cis-CH2CH2CH2CH3), 14.03 (trans-CH2CH2CH2CH3), 20.21
(cis-C5H2), 22.74 (trans-C5H2), 22.83, 23.42 (CH2CH2CH2CH3), 24.
24 (cis-C4H2), 24.74 (trans-C4H2), 25.31 (cis-C3H2), 28.45 (trans-
C3H2), 29.23, 29.40, 29.73, 30.12 (CH2CH2CH2CH3), (CH2CH2-
CH2CH3), 37.50 (cis-C6H2), 39.05 (trans-C6H2), 44.19 (cis-C2H), 46.
66 (trans-C2H), 71.47 (cis-C1), 74.23 (trans-C1), 120.50 (trans-CN),
122.61 (cis-CN)
3
rac-2f
0.91 (t, JZ7.1, 2H, trans-CH2CH2CH2CH3), 0.92 (t, 3JZ7.0, 1H,
cis-CH2CH2CH2CH3), 1.11–1.47 (m, 7H, 3CH, CH2CH2CH2CH3,
CH2CH2CH2CH3), 1.52–1.95 (m, 7H, 7CH), 2.09–2.23 (m, 1H,
C6Heq), 2.45 and 2.90 (br s, 1H, OH)
rac-5a
rac-5b
rac-5c
1.19–1.97 (m, 6H, 6CH), 2.14–2.26 (m, 2H, C6Hax, C6Heq), 3.13 (dd,
19.59 (cis-C5H2), 22.38 (C4H2), 23.24 (trans-C5H2), 25.19 (cis-
C3H2), 26.85 (trans-C3H2), 35.01 (cis-C6H2), 35.40 (trans-C6H2), 56.
88 (trans-OCH3), 57.60 (cis-OCH3), 69.94 (cis-C1), 73.92 (trans-C1),
81.18 (cis-C2H), 84.24 (trans-C2H), 119.75 (trans-CN), 121.79 (cis-
CN)
3
3J (C2Hax, C3Heq)Z4.1 Hz, J (C2Hax, C3Hax)Z11.0, 0.6H, trans-
C2Hax), 3.39 (dd, 3J (C2Hax, C3Heq)Z4.4, 3J (C2Hax, C3Hax)Z10.1,
0.4H, cis-C2Hax), 3.46 and 3.52 (s, 3H, OCH3), 3.70 (br s, 1H, OH)
1.22–1.96 (m, 6H, 6CH), 1.25 (t, 3JZ7.0, 3H, OCH2CH3), 2.10–2.25
15.38 (OCH2CH3), 15.47 (OCH2CH3), 19.54 (C5H2), 22.39 (C4H2),
22.58 (C4H2), 23.37 (C5H2), 26.12 (C3H2), 27.68 (C3H2), 35.02
(C6H2), 35.34 (C6H2), 64.62 (OCH2CH3), 65.64 (OCH2CH3), 70.10
(C1), 73.91 (C1), 79.38 (C2H), 82.61 (C2H), 119.87 (CN), 121.91
(CN)
10.53 (OCH2CH2CH3), 19.60, 22.39, 22.51, 23.08, 23.17, 23.34
(C5H2), (C4H2), (OCH2CH2CH3), 26.02 (cis-C3H2), 27.58 (trans-
C3H2), 35.01 (cis-C6H2), 35.31 (trans-C6H2), 70.12 (trans-OCH2-
CH2CH3), 70.82 (cis-OCH2CH2CH3), 71.83 (cis-C1), 74.03 (trans-
C1), 79.54 (cis-C2H), 82.73 (trans-C2H), 119.85 (trans-CN), 121.88
(cis-CN)
(m, 2H, C6Hax, C6Heq), 3.21 (dd, 3J (C2Hax, C3Heq)Z4.2, 3J (C2Hax
,
C3Hax)Z11.1, 0.5H, C2Hax), 3.40–3.52 (m, 0.5H, C2Hax), 3.62–3.83
(m, 3H, OCH2CH3, OH)
3
0.95 (t, JZ7.4, 1.5H, OCH2CH2CH3), 0.96 (t, 3JZ7.4, 1.5H,
OCH2CH2CH3), 1.21–1.31 (m, 1H, OCH2CH2CH3), 1.42–1.90(m,
7H, 6CH, OCH2CH2CH3), 2.09–2.24 (m, 2H, C6Hax, C6Heq), 3.19
(dd, 3J (C2Hax, C3Heq)Z4.2, 3J (C2Hax, C3Hax)Z11.3, 0.5H, C2Hax),
3.23 (bs, 0.5H, OH), 3.33–3.38 (m, 0.5H, OCHAHCH2CH3), 3.46 (dd,
3J (C2Hax, C3Heq)Z4.5, 3J (C2Hax, C3Hax)Z10.2, 0.5H, C2Hax), 3.
55–3.66 (m, 2H, OCHAHCH2CH3, OH, OCHHBCH2CH3)
rac-5d
1.17–1.24 (m, 6H, OCH(CH3)2), 1.42–1.83 (m, 6H, 6CH), 2.02–2.09
(m, 1H, C6Hax, C6Heq), 2.25–2.35 (m, 1H, C6Hax, C6Heq), 3.22–3.28
19.42, 21.87, 22.31, 22.38, 22.82, 23.09, 23.41, 23.54 (C5H2),
(C4H2), (OCH(CH3)2)*), 27.19 (cis-C3H2), 28.54 (trans-C3H2), 35.01
(cis-C6H2), 35.28 (trans-C6H2), 70.08 (trans-OCH(CH3)2), 70.35
(cis-OCH(CH3)2), 71.66 (cis-C1), 73.94 (trans-C1), 77.26 (cis-C2H),
80.33 (trans-C2H), 119.95 (trans-CN), 122.01 (cis-CN)*) rotamers
(br s, 0.5H, OH), 3.24 (dd, 3J (C2Hax, C3Heq)Z4.1 Hz, 3J (C2Hax
,
C3Hax)Z10.8, 0.5H, C2Hax), 3.51 (dd, 3J (C2Hax, C3Heq)Z4.2 Hz, 3J
(C2Hax, C3Hax)Z10.2, 0.5H, C2Hax), 3.60 (br s, 0.5H, OH), 3.78
(sept, 3JZ6.1, 0.4H, trans-OCH(CH3)2), 3.91 (sept, 3JZ5.9, 0.6H,
cis-OCH(CH3)2)
rac-5e
rac-7a
1.43–1.88 (m, 6H, 6CH), 2.09–2.14 (m, 1H, CH), 2.21–2.27 (m, 1H,
CH), 3.21 (br s, 0.5H, OH), 3.25–3.29 (m, 0.5H, C2Hax), 3.52–3.55
(m, 0.5H, C2Hax), 3.63 (br s, 0.5H, OH), 3.99–4.03 (m, 0.5H,
OCHAHCH]CH2), 4.15–4.25 (m, 1.5H, OCHAHCH]CH2,
OCHHBCH]CH2), 5.22-5.24 (m, 1H, OCH2CH]CHAH), 5.30–5.
34 (m, 1H, OCH2CH]CHHB), 5.88–5.98 (m, 1H, OCH2CH]CH2)
0.82–1.04 (m, 1H, CH), 0.92 (d, 3JZ6.4 Hz, 0.5H, trans-CH3), 0.98
(d, 3JZ6.3 Hz, 2.5H, cis-CH3), 1.16–1.26 (m, 1H, CH), 1.38–1.90
(m, 5H, 5CH), 2.06–2.21 (m, 2H, C2Heq, C6Heq), 3.14 (br s, 1H, OH)
19.53, 22.37, 22.55, 23.33 (C5H2), (C4H2), 26.09 (cis-C3H2), 27.70
(trans-C3H2), 35.08 (cis-C6H2), 35.44 (trans-C6H2), 70.05, 70.87
(OCH2CH]CH2), 70.13 (cis-C1), 73.95 (trans-C1), 78.75 (cis-C2H),
82.11 (trans-C2H), 117.88, 118.02 (OCH2CH]CH2), 119.76 (trans-
CN), 121.81 (cis-CN), 134.14, 134.21 (OCH2CH]CH2)
19.89 (trans-C5H2), 21.64 (cis-C5H2), 21.80 (trans-CH3), 22.91 (cis-
CH3), 26.25 (trans-C3H), 30.14 (cis-C3H), 33.19 (trans-C4H2), 33.39
(cis-C4H2), 36.21 (trans-C6H2), 37.78 (cis-C6H2), 44.48 (trans-
C2H2), 46.15 (cis-C2H2), 67.25 (trans-C1), 70.54 (cis-C1), 121.89
(cis-CN), 122.95 (trans-CN)