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Y. Suzuki et al. / Tetrahedron 62 (2006) 4227–4231
4.2. Typical procedure for cyanosilylation of aldehydes
a-Acetyloxy-1-(2-methoxynaphthalene)acetonitrile: color-
less prisms (recrystallized from CH2Cl2/hexane); Mp 133–
135 8C; 1H NMR (CDCl3) d: 2.14 (3H, s, CH3), 4.03 (3H, s,
OCH3), 7.28 (1H, d, JZ9.2 Hz), 7.42–7.45 (1H, m), 7.53
(1H, s, CHOAc), 7.60–7.63 (1H, m), 7.83 (1H, d, JZ
8.0 Hz), 7.95 (1H, d, JZ9.2 Hz), 8.25 (1H, d, JZ8.6 Hz);
13C NMR (CDCl3) d: 20.6, 55.1, 56.9, 112.2, 112.9, 116.9,
123.3, 124.4, 128.1, 129.0, 129.3, 131.8, 133.3, 155.6,
169.1; IR (KBr) 1749 (CO) cmK1; HRMS (FAB) Calcd for
C15H13NO3 (MC): 255.0895, found: 255.0875; Analytical
chiral HPLC: Chiralcel OD-H column, 0.46!25 cm,
hexane–2-propanol (98/2), 0.5 mL minK1; 29.9, 40.3 min.
To a suspension of azolium salt (0.05 mmol) in THF (2 mL),
1 M t-BuOK/THF (0.05 mmol) was added at room
temperature, and the mixture was stirred for 30 min.
Subsequently, the aldehyde (1 mmol) and TMS-CN
(1.1 mmol) were added. This mixture was stirred at room
temperature for the indicated time and then treated with
dilute HCl. The crude product was extracted with ethyl
acetate. The organic layer was dried over MgSO4 and
evaporated. The residue was purified by silica gel
chromatography using hexane/ethyl acetate as an eluent in
order to produce cyanohydrin.
4.2.6. 2-Hydroxy-4-phenyl-3-butenenitrile (8f).22 Pale
yellow powder (recrystallized from CH2Cl2/hexane); Mp
The enantiomeric excess of 8a,e was determined by chiral
HPLC analysis after the conversion to acetate.
1
71–74 8C; H NMR (CDCl3) d: 2.65 (1H, d, JZ6.3 Hz,
CHOH), 5.17 (1H, t, JZ6.3 Hz, CHOH), 6.26 (1H, dd, JZ
16.0, 6.3 Hz, olefinic H), 6.92 (1H, dd, JZ16.0, 1.1 Hz,
olefinic H), 7.30–7.40 (3H, m), 7.42 (2H, d, JZ8.6 Hz); 13C
NMR (CDCl3) d: 62.0, 118.4, 122.3, 127.2, 129.0, 129.2,
4.2.1. 4-Chloromandelonitrile (8a).21 Colorless granules
(recrystallized from CHCl3/hexane); Mp 35–37 8C; 1H
NMR (CDCl3) d: 3.16 (1H, br s, CHOH), 5.52 (1H, s,
CHOH), 7.41 (2H, d, JZ8.6 Hz), 7.46 (2H, d, JZ8.6 Hz);
13C NMR (CDCl3) d: 63.0, 118.5, 128.1, 129.5, 133.6,
134.8, 135.4; IR (KBr) 2253 (CN), 3358 (OH) cmK1
.
136.1; IR (KBr) 2255 (CN), 3401 (OH) cmK1
.
4.2.7. 2-Hydroxyoctanenitrile (8g).23 Yellow oil; 1H NMR
(CDCl3) d: 0.87 (3H, t, JZ6.9 Hz, Me), 1.24–1.38 (6H, m),
1.44–1.50 (2H, m), 1.81 (2H, q, JZ6.9 Hz), 3.64 (1H, br s,
CHOH), 4.44 (1H, t, JZ6.9 Hz, CHOH); 13C NMR (CDCl3)
d: 14.1, 22.6, 24.6, 28.7, 31.6, 35.2, 61.3, 120.3; IR (neat)
4-Chloromandelonitrile, acetate: Analytical chiral HPLC:
Chiralcel OD-H column, 0.46!25 cm, hexane–2-propanol
(99/1), 0.5 mL minK1; 21.5, 25.2 min.
2247 (CN), 3447 (OH) cmK1
.
1
4.2.2. 4-Methoxymandelonitrile (8b).22 Colorless oil; H
4.2.8. 2-Cyclohexyl-2-hydroxyacetonitrile (8h).21 Color-
less oil; 1H NMR (CDCl3) d: 1.01–1.28 (5H, m), 1.62–1.89
(6H, m), 3.87 (1H, br s, CHOH), 4.22 (1H, dd, JZ6.3,
5.7 Hz, CHOH); 13C NMR (CDCl3) d: 25.5, 25.5, 26.0,
27.9, 28.2, 42.2, 66.2, 119.6; IR (neat) 2245 (CN), 3435
NMR (CDCl3) d: 3.81 (3H, s, OCH3), 5.44 (1H, s, CHOH),
6.92 (2H, d, JZ4.6 Hz), 7.42 (2H, d, JZ4.6 Hz); 13C NMR
(CDCl3) d: 55.5, 63.2, 114.5, 119.3, 127.8, 128.4, 160.6; IR
(neat) 2245 (CN), 3414 (OH) cmK1
.
4.2.3. 2-Methoxymandelonitrile (8c).22 Colorless granules
(recrystallized from CH2Cl2/hexane); Mp 64–67 8C; 1H
NMR (CDCl3) d: 3.62 (1H, d, JZ8.9 Hz, CHOH), 3.94 (3H,
s, OCH3), 5.56 (1H, d, JZ8.9 Hz, CHOH), 6.97 (1H, d, JZ
8.6 Hz), 7.01 (1H, t, JZ7.5 Hz), 7.38–7.42 (2H, m); 13C
NMR (CDCl3) d: 55.9, 60.4, 111.3, 119.0, 121.2, 123.8,
(OH) cmK1
.
4.2.9. 2-Hydroxy-3,3-dimethylbutanenitrile (8i).24
1
Yellow oil; H NMR (CDCl3) d: 1.05 (9H, s, CH3), 3.28
(1H, br s, CHOH), 4.11 (1H, s, CHOH). 13C NMR (CDCl3)
d: 25.0, 35.5, 70.6, 119.3.
128.2, 131.3, 156.8; IR (KBr) 2251 (CN), 3377 (OH) cmK1
.
4.2.4. a-Hydroxy-1-naphthaleneacetonitrile (8d).21
1
Yellow oil; H NMR (CDCl3) d: 2.93 (1H, d, JZ6.3 Hz,
References and notes
CHOH), 6.18 (1H, d, JZ6.3 Hz, CHOH), 7.51 (1H, dd, JZ
8.0, 7.5 Hz), 7.57 (1H, dd, JZ8.0, 6.9 Hz), 7.61–7.64 (1H,
m), 7.83 (1H, d, JZ7.5 Hz), 7.91 (1H, d, JZ8.6 Hz), 7.94
(1H, d, JZ8.0 Hz), 8.15 (1H, d, JZ8.6 Hz); 13C NMR
(CDCl3) d: 62.2, 119.0, 123.0, 125.3, 125.8, 126.6, 127.5,
129.1, 130.0, 130.3, 131.0, 134.0; IR (neat) 2249 (CN),
1. (a) Evans, D. A.; Truesdale, L. K.; Carroll, G. L. J. Chem. Soc.,
Chem. Commun. 1973, 55–56. (b) Ledy, W.; Sundermeyer, W.
Chem. Ber. 1973, 106, 587–593.
2. (a) Evans, D. A.; Wong, R. Y. J. Org. Chem. 1977, 42,
350–352. (b) Kobayashi, S.; Tsuchiya, Y.; Mukaiyama, T.
Chem. Lett. 1991, 537–540.
3399 (OH) cmK1
.
4.2.5. a-Hydroxy-1-(2-methoxynaphthalene)acetonitrile
(8e). Colorless needles (recrystallized from CH2Cl2/hex-
ane); Mp 95–97 8C; H NMR (CDCl3) d: 3.94 (1H, d, JZ
3. (a) Herrmann, W. A. Angew. Chem., Int. Ed. 2002,
41, 1290–1309. (b) Herrmann, W. A.; Weskamp, T.;
Bohm, V. P. W. Adv. Organomet. Chem. 2001, 48, 1–69.
(c) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34,
18–29.
1
9.7 Hz, CHOH), 4.09 (3H, s, OCH3), 6.34 (1H, d, JZ
9.7 Hz, CHOH), 7.32 (1H, d, JZ9.2 Hz), 7.41–7.44 (1H,
m), 7.58–7.61 (1H, m), 7.84 (1H, d, JZ8.0 Hz), 7.94 (1H, d,
JZ9.2 Hz), 8.04 (1H, d, JZ8.6 Hz); 13C NMR (CDCl3) d:
56.6, 56.9, 112.9, 116.4, 119.3, 121.8, 124.5, 128.4, 129.1,
129.4, 130.8, 132.4, 155.6; IR (KBr) 2241 (CN), 3453
(OH) cmK1; HRMS (FAB) Calcd for C13H11NO2 (MC):
213.0790, found: 213.0814.
4. (a) Ukai, T.; Tanaka, R.; Dokawa, T. J. Pharm. Soc. Jpn. 1943,
63, 296–300. (b) Ukai, T.; Dokawa, T.; Tsubokawa, S.
J. Pharm. Soc. Jpn. 1944, 64, 3–4. (c) Breslow, R. J. Am.
Chem. Soc. 1958, 80, 3719–3726.
5. (a) Miyashita, A.; Suzuki, Y.; Kobayashi, M.; Kuriyama, N.;
Higashino, T. Heterocycles 1996, 43, 509–512. (b) Miyashita, A.;