88 J . Org. Chem., Vol. 65, No. 1, 2000
Ta ble 4. Kin etic Resolu tion of (()-10 by a On e-P ot P r oced u r e (Meth od B)a
Kita et al.
a
b
Results by method A are cited from Table 1. The ee value for 10 was determined by HPLC using Daicel CHIRALCEL OD (hexane-
i-PrOH). The ee value for 11 was determined after saponification of 11 into corresponding 10 otherwise noted. c Th ee value was determined
after conversion to the corresponding 3,5-dinitrobenzoate. Conversion of 11h to the 3,5-dinitrobenzoate was run by saponification followed
by esterification.
(S)-1-(4-Ch lor op h en yl)eth a n ol (10c): [R]22D -49.6 (Et2O,
(R)-6-Meth yl-5-h ep ten -2-yl Octa n oa te (11h ): 1H NMR
(300 MHz, CDCl3) δ 0.88 (3H, t, J ) 6.0 Hz), 1.20-1.40 (11H,
m) 1.40-1.75 (10H, m), 2.00 (2H, q, J ) 7.0 Hz), 2.26 (2H, t,
J ) 7.0 Hz), 4.80-4.95 (1H, m), 5.00-5.10 (1H, m); IR (CHCl3)
c 1.8) {lit.21 [R]21 +46.1 (Et2O, c 0.9-1.1) for 91% ee of the
D
1
(R)-form}; H NMR (200 MHz, CDCl3) δ 1.48 (3H, d, J ) 6.5
Hz), 1.81 (1H, d, J ) 3.5 Hz), 4.89 (1H, dd, J ) 6.5, 3.5 Hz),
7.31 (4H, s); IR (KBr) 3329 cm-1
.
1720 cm-1
.
(R)-1-(4-Ch lor op h en yl)eth yl Aceta te (11c): 1H NMR
(200 MHz, CDCl3) δ 1.51 (3H, d, J ) 6.5 Hz), 2.06 (3H, s),
5.83 (1H, q, J ) 6.5 Hz), 7.29-7.35 (4H, m); IR (KBr) 1740
(S)-1-Octyn -3-ol (10h ): [R]24 -6.0 (pentane, c 1.0) {lit.24
D
[R]20D -3.57 (pentane, c 5.39) for 21% ee}; 1H NMR (300 MHz,
CDCl3) δ 0.90 (3H, t, J ) 6.5 Hz), 1.30-1.80 (9H, m), 2.47 (1H,
cm-1
.
d, J ) 2.0 Hz), 4.30-4.40 (1H, m); IR (CHCl3) 3300 cm-1
.
(S)-1-P h en yl-1-p r op a n ol (10d ): [R]22D -43.9 (CHCl3, c 1.7)
{lit.20 [R]D -47.6 (CHCl3, c 6.1) for 98% ee}; 1H NMR (200 MHz,
CDCl3) δ 0.93 (3H, t, J ) 7.5 Hz), 1.70-1.90 (3H, m), 4.55-
(R)-1-Octyn -3-yl Octa n oa te (11i): [R]24D -36.9 (pentane,
1
c 1.1); H NMR (300 MHz, CDCl3) δ 0.88 (3H, t, J ) 7.0 Hz),
0.90 (3H, t, J ) 6.5 Hz), 1.30-1.80 (18H, m), 2.33 (2H, t, J )
7.5 Hz), 2.44 (1H, d, J ) 2.0 Hz), 5.36 (1H, td, J ) 6.5, 2.0
Hz); IR (CHCl3) 1732 cm-1. Anal. Calcd for C16H28O2: C, 76.14;
H, 11.18. Found: C, 76.12; H, 11.13.
4.68 (1H, m), 7.20-7.40 (5H, m); IR (KBr) 3354 cm-1
.
(R)-1-P h en yl-1-p r op yl Aceta te (11d ): 1H NMR (200
MHz, CDCl3) δ 0.88 (3H, t, J ) 7.5 Hz), 1.78-1.95 (2H, m),
2.08 (3H, s), 5.66 (1H, t, J ) 7.5 Hz), 7.30-7.34 (5H, m); IR
Lip a se-Ca ta lyzed Kin etic Resolu tion of (()-10a by a
On e-P ot P r oced u r e. Typ ica l P r oced u r e for Meth od B.
To an ice-cooled solution of ethoxyacetylene (168 mg, 2.1 mmol)
and [RuCl2(p-cymene)]2 (3.9 mg, 6.4 µmol) in anhydrous i-Pr2O
(2.2 mL) was added dropwise a solution of acetic acid (96 mg,
1.6 mmol) in anhydrous i-Pr2O (0.8 mL). The reaction mixture
was stirred at 0 °C for 0.5 h, warmed to room temperature,
and stirred for an additional 1 h. This mixture was added to
a mixture of (()-10a (244 mg, 2.0 mmol) and lipase PS-D (80
mg) in anhydrous i-Pr2O (2.9 mL). The remainder of the
procedure is the same as described in method A to give (S)-
10a (109 mg, 45%, >99% ee) and (R)-11a (152 mg, 46%, 96%
ee). The reaction conditions, isolated yields, and optical purity
of the products 10 and 11 for other cases are summarized in
Table 4. All products obtained by this method are identical,
except for the optical purity, with the compounds obtained by
(KBr) 1736 cm-1
.
(R)-2-Ch lor o-1-p h en yleth a n ol (10e): [R]22 -58.9 (c-
D
C6H12, c 1.3) {lit.22 [R]D +53.3 (c-C6H12, c 2) for the (S)-form};
1H NMR (200 MHz, CDCl3) δ 2.65 (1H, d, J ) 3.0 Hz), 3.60-
3.80 (2H, m), 4.86-4.96 (1H, m), 7.26-7.43 (5H, m); IR (KBr)
3320 cm-1
.
(S)-2-Ch lor o-1-p h en yleth yl Aceta te (11e): 1H NMR (200
MHz, CDCl3) δ 2.14 (3H, s), 3.60-3.90 (2H, m), 5.96 (1H, dd,
J ) 7.5, 5.0 Hz), 7.37 (5H, s); IR (KBr) 1748 cm-1
.
(S)-1-In d a n ol (10f): [R]22 +30.8 (CHCl3, c 0.8) {lit.23 [R]D
D
1
+24.4 (CHCl3, c 2) for 71% ee}; H NMR (200 MHz, CDCl3) δ
1.70 (1H, d, J ) 7.0 Hz), 1.87-2.03 (1H, m), 2.42-2.58 (1H,
m), 2.75-2.90 (1H, m), 3.00-3.12 (1H, m), 5.21-5.30 (1H, m),
7.21-7.45 (4H, m); IR (KBr) 3339 cm-1
.
(R)-1-In d a n yl Aceta te (11f): 1H NMR (200 MHz, CDCl3)
δ 2.00-2.43 (1H, m), 2.06 (3H, s), 2.43-2.54 (1H, m), 2.82-
2.93 (1H, m), 3.05-3.15 (1H, m), 6.20 (1H, dd, J ) 4.0, 7.0
method A. 10a (run 1), [R]24 -54.1 (c-C5H10, c 1.8); 10a (run
D
2), [R]23D -50.3 (c-C5H10, c 1.9); 10g (run 3); [R]22D +13.1 (EtOH,
Hz), 7.12-7.43 (4H, m); IR (KBr) 1734 cm-1
.
c 1.0).
(S)-6-Meth yl-5-h ep ten -2-ol (10g): [R]22 +14.0 (EtOH, c
D
0.7) {lit.11 [R]D +16.6 (EtOH, c 1.0) for 99.9% ee}; 1H NMR
(250 MHz, CDCl3) δ 1.19 (3H, d, J ) 7.0 Hz), 1.38-1.60 (2H,
m), 1.63 (3H, s), 1.69 (3H, s), 1.90-2.20 (2H, m), 3.70-3.85
Ack n ow led gm en t. This work was supported by a
Grant-in-Aid for Scientific Research No. 09557180 from
the Ministry of Education, Science, Sports, and Culture,
J apan. We thank Noriyuki Kawano for technical as-
sistance. Amano Pharmaceutical Co., Ltd., J apan, and
Roche Diagnostics K. K., J apan, are thanked for their
generous gifts of lipases.
(1H, m), 5.05-5.20 (1H, m); IR (CHCl3) 3611 cm-1
.
(R)-6-Meth yl-5-h ep ten -2-yl Aceta te (11g): 1H NMR (200
MHz, CDCl3) δ 1.21 (3H, d, J ) 5.0 Hz), 1.40-1.70 (2H, m),
1.60 (3H, s), 1.68 (3H, s), 1.90-2.10 (2H, m), 2.03 (3H, s), 4.80-
4.95 (1H, m), 5.00-5.12 (1H, m); IR (CHCl3) 1724 cm-1
.
J O9910785
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