The mixture was filtered, and the resin and the filtrate were
extracted with ether separately. The ethereal solutions were
collected, dried over anhydrous magnesium sulfate, and
concentrated in vacuo. The residue was subjected to column
chromatography (silica gel, hexane–AcOEt = 10:1), and the
crude product was subjected to bulb-to-bulb distillation (23
mmHg, 150 ЊC) to afford (S)-nonan-2-ol (211 mg, 1.46 mmol,
66% yield, >99% ee). After a part of the nonan-2-ol was
acetylated with acetyl chloride and triethylamine, the ee was
determined by GLC analysis, and the absolute configuration
was determined by comparing its optical rotations with that
reported. [α]D ϩ7.9 (c = 0.86, CHCl3) (lit.5 [α]D ϩ7.96 (CHCl3)),
References
1 S. M. Roberts, J. Chem. Soc., Perkin Trans. 1, 2000, 611; S. M.
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Reagents in Organic Synthesis, ed. S. Servi, Kluwer Academic
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1
97% ee (S); H-NMR (200 MHz, CDCl3) δ 0.87 (m, 3H), 1.17
(d, 3H, J = 6.2 Hz), 1.21–1.55 (m, 12 H), 1.84 (s, 1H), 3.77 (m,
1H); IR (neat) ν 3353, 2961, 2880, 2857, 1464, 1375, 1306, 1211,
1115, 1076, 930, 849 cmϪ1
.
(S)-2-Methylhept-2-en-6-ol. The cells (15 g wet wt) were
added to a mixture of 2-methylhept-2-en-6-one (308 mg, 2.44
mmol) and XAD-7 (18 g) in water (90 mL), and shaken at 130
rpm for 1 day at 30 ЊC. The mixture was filtered, and the resin
and the filtrate were extracted with ether separately. The ethereal
solutions were collected, dried over anhydrous magnesium
sulfate, and concentrated in vacuo. The residue was subjected to
column chromatography (silica gel, hexane–AcOEt = 10:1),
and the crude product was subjected to bulb-to-bulb distillation
(25 mmHg, 150 ЊC) to afford (S)-2-methylhept-2-en-6-ol
(200 mg, 1.58 mmol, 65% yield, 98% ee). The ee was determined
by GLC analysis, and the absolute configuration was deter-
mined by comparing its optical rotations with that reported.
[α]D ϩ11.2 (c = 0.84, CHCl3) (lit.5 [α]D ϩ10.76 (CHCl3)),
99% ee (S); 1H-NMR (200 MHz, CDCl3) δ 1.17 (d, 3H, J = 6.2
Hz), 1.45 (m, 2H), 1.60 (s, 3H), 1.67 (d, 3H, J = 1.2 Hz), 1.70
(m, 1H), 2.05 (m, 2H), 3.78 (m, 1H), 5.11 (m, 1H); IR
(neat) ν 3358, 2969, 2926, 2361, 1451, 1377, 1173, 1127,
1074, 1061, 990, 953, 907, 856, 826 cmϪ1. Anal. Calcd. for
C8H16O C 74.94, H 12.58, O: 12.48%. Found C 74.94, H 12.58,
O 12.68%.
2 J. Davis and J. B. Jones, J. Am. Chem. Soc., 1979, 101, 5401;
J. Haslegrave and J. B. Jones, J. Am. Chem. Soc., 1982, 104, 4666.
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633.
4 E. Keinan, E. K. Hafeli, K. K. Seth and R. Lamed, J. Am. Chem.
Soc., 1986, 108, 162; E. Keinan, K. Seth and R. Lamed, J. Am.
Chem. Soc. 1986, 108, 3474.
5 K. Nakamura, T. Yoneda, T. Miyai, K. Ushio, S. Oka and A. Ohno,
Tetrahedron Lett., 1988, 29, 2453; K. Nakamura, S. Takano,
K. Terada and A. Ohno, Chem. Lett., 1992, 951.
6 C. W. Bradshaw, H. Fu, G.-J. Shen and C.-H. Wong, J. Org. Chem.,
1992, 57, 1526; C. W. Bradshaw, W. Hummel and C.-H. Wong,
J. Org. Chem., 1992, 57, 1532; R. N. Patel, C. G. McNamee, A.
Banerjee, J. M. Howell, R. S. Robinson, L. J. Szarka, Enzyme
Microb. Technol., 1992, 14, 731.
7 K. Nakamura, S. Kondo, Y. Kawai, N. Nakajima and A. Ohno,
Biosci. Biotechnol. Biochem., 1994, 58, 2236; K. Nakamura,
Y. Kawai, N. Nakajima and A. Ohno, J. Org. Chem., 1991, 56, 4778;
W.-R. Shieh, A. S. Gopalan and C. J. Sih, J. Am. Chem. Soc., 1985,
107, 2993.
8 B. A. Anderson, M. M. Hansen, A. R. Harkness, C. L. Henry,
J. T. Vicenti and M. J. Zmijewsky, J. Am. Chem. Soc., 1995, 117,
12358.
9 P. D’Arrigo, C. Fuganti, S. Servi and A. Strini, Tetrahedron:
Asymmetry, 1997, 8, 2375; P. D’Arrigo, C. Fuganti, G. P. Fantoni
and S. Servi, Tetrahedron, 1998, 54, 15017.
10 (a) K. Nakamura, Y. Inoue, T. Matsuda and I. Misawa, J. Chem.
Soc., Perkin Trans. 1, 1999, 2397; (b) D. Buisson, R. Azerad,
C. Sanner and M. Larcheveque, Biocatalysis, 1992, 5, 249.
11 S. A. Weissman and P. V. Ramachandran, Tetrahedron Lett., 1996,
37, 3791.
(S)-6-Methylheptan-2-ol. The cells (15 g wet wt) were added
to a mixture of 6-methylheptan-2-one (310 mg, 2.42 mmol) and
XAD-7 (18 g) in water (90 mL), and shaken at 130 rpm for 1
day at 30 ЊC. The mixture was filtered, and the resin and the
filtrate were extracted with ether separately. The ethereal solu-
tions were collected, dried over anhydrous magnesium sulfate,
and concentrated in vacuo. The residue was subjected to column
chromatography (silica gel, hexane–AcOEt = 10:1), and the
crude product was subjected to bulb-to-bulb distillation (25
mmHg, 150 ЊC) to afford (S)-6-methylheptan-2-ol (109 mg,
0.837 mmol, 35% yield, >99% ee). The ee was determined by
GLC analysis. The absolute configuration was determined by
comparing its retention time with that of authentic sample
which was obtained by palladium-black mediated hydrogen-
ation of (S)-2-methylhept-2-en-6-ol. [α]D ϩ8.7 (c = 0.72,
12 R. Noyori, I. Tomino, Y. Tanimoto and M. Nishizawa, J. Am. Chem.
Soc., 1984, 106, 6709.
13 R. Macleod, H. Prosser, L. Finkentsher, J. Lanyi and H. S. Mosher,
Biochemistry, 1964, 3, 838.
14 K. Nakamura, Y. Inoue and A. Ohno, Tetrahedron Lett., 1994, 35,
4375.
15 K. Nakamura, Y. Inoue, T. Matsuda and A. Ohno, Tetrahedron
Lett., 1995, 36, 6263.
16 K. Nakamura, T. Matsuda and A. Ohno, Tetrahedron: Asymmetry,
1996, 7, 3921.
17 (a) K. Nakamura, S. Kondo, N. Nakajima, A. Ohno, Tetrahedron,
1995, 51, 687; (b) K. Nakamura, S. Kondo, Y. Kawai and A. Ohno,
Bull. Chem. Soc. Jpn., 1993, 66, 2738; (c) K. Nakamura, S. Kondo,
Y. Kawai and A. Ohno, Tetrahedron Lett., 1991, 32, 7075.
18 XAD was also used to immobilize hydrolytic enzymes in hydrolysis
and ester and peptide formation: (a) (hydrolysis) E. Battistel,
D. Bianchi, P. Cesti and C. Pina, Biotechnol. Bioeng., 1991, 38, 659;
(b) (ester formation) S.-H. Hsu, S.-S. Wu, Y. F. Wang and C.-H.
Wong, Tetrahedron Lett., 1990, 31, 6403; (c) (peptide formation)
K. Oyama, S. Nishimura, Y. Nonaka, K. Kihara and T. Hashimoto,
J. Org. Chem., 1981, 46, 5241.
1
CHCl3); H-NMR (200 MHz, CDCl3) δ 0.86 (d, 6H, J = 6.6
Hz), 1.11–1.60 (m, 9H), 3.78 (m, 1H); IR (neat) ν 3345, 2957,
2932, 2870, 1466, 1367, 1337, 1202, 1148, 1117, 1017, 972, 931,
856 cmϪ1
.
Hydrogenation of (S)-2-methylhept-2-en-6-ol
Palladium-black (10 mg) was added to a solution of (S)-2-
methylhept-2-en-6-ol (0.16 mmol, 98% ee) in acetic acid (1 mL),
and the resulting mixture was stirred for 6 h at room temperature
under a hydrogen atmosphere at atmospheric pressure. The
mixture was put on to silica gel, and eluted with ether. The
yield and ee of the product were determined by GLC analysis;
(S)-6-methylheptan-2-ol (87% yield, 98% ee) was assigned as
the first fraction (26.7 min) by comparing its retention time
with that of a racemic sample. The absolute configuration of
hex-5-en-2-ol was determined by the same method.
19 K. Nakamura, M. Kawasaki and A. Ohno, Bull. Chem. Soc. Jpn.,
1996, 69, 1079.
20 R. Seemayer and M. P. Schneider, Tetrahedron: Asymmetry, 1992, 3,
827.
21 J. Uenishi, T. Hiraoka, S. Hata, K. Nishiwaki, O. Yonemitsu,
K. Nakamura and H. Tsukube, J. Org. Chem., 1998, 63, 1581.
22 V. Waagen, V. Partali, I. Hollingsaeter, M. S. S Huang and
T. Anthonsen, Acta Chem. Scand., 1994, 48, 506.
23 H. Ohta, Y. Kato and G. Tsuchihashi, J. Org. Chem., 1987, 52, 2735.
J. Chem. Soc., Perkin Trans. 1, 2000, 3205–3211
3211