2
272 Bull. Chem. Soc. Jpn., 77, No. 12 (2004)
Cyanobacterium-Catalyzed Reduction of Enones
2
D
5
was added. The transformation was performed by incubating the
ꢄ
duction of 26a–30a and 31 were the following. 26b: ½ꢀꢁ þ13:5
25 20
19
mixture at 25 C for 1 or 3 days on a rotary shaker (70 rpm) under
(c 0.37, CHCl3); 27b: ½ꢀꢁ þ13:1 (c 0.33, CHCl3) {lit. : ½ꢀꢁ
D
25 20
D
19
illumination (4000 lux). The incubation product was extracted
with ether and was subjected to chromatography on silica gel with
pentane–ethyl acetate (95:5, v/v) to separate the products. The
product ketones were identified by comparisons of their TLC,
GLC, and GC–MS data with those of authentic samples.3,9,14
The absolute configurations and optical purities of the resulting
ketones 17, 18, 19a, 20, and 21 were determined by optical rota-
tion or circular dichroism (CD) analyses and the peak area of the
corresponding enantiomers by GLC analyses on CP cyclodextrin
þ10:3}; 28b: ½ꢀꢁ þ10:9 (c 0.45, CHCl3) {lit. : ½ꢀꢁ þ10:4};
D
25 20
D
19
29b: ½ꢀꢁ þ10:4 (c 0.52, CHCl3) {lit. : ½ꢀꢁ þ10:2}; 30b:
D
D
2
D
5
19
20
D
25
D
½ꢀꢁ þ8:7 (c 0.50, CHCl3) {lit. : ½ꢀꢁ þ8:5}; 19b: ½ꢀꢁ
2
0
20
D
25
D
þ50:4 (c 0.26, CHCl3) {lit. : ½ꢀꢁ þ42:9}; 19c: ½ꢀꢁ þ25:2
20
20
(c 0.24, CHCl3) {lit. : ½ꢀꢁ þ24:3}.
D
The authors thank the Research Laboratory Center of Oita
University for the measurements of 1H NMR and GC–MS
spectra. This work was supported in part by a Grant-in-Aid
for Scientific Research (No. 16790014) from the Ministry of
Education, Culture, Sports, Science and Technology.
ꢁ
236M-19 column. In order to obtain the products adequate for
identification by optical rotation or CD analysis, we scaled up
the incubation of substrates with the cells by 10-fold in a similar
manner to the standard biotransformation system. Diastereomeric
excesses of 22 and 23 were also determined from the peak areas of
the corresponding diastereomers by GLC analyses. Retention
times for the products in the GLC were as follows: (S)- and (R)-
References
1
K. Tomioka and K. Koga, ‘‘Asymmetric Synthesis,’’ ed by
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a) A. Kergomard, M. F. Renard, and H. Veschambre,
1
7, 10.5 and 11.4 min; (S)- and (R)-18, 12.1 and 12.9 min; (S)-
2
and (R)-19a, 11.8 and 12.8 min; (S)- and (R)-20, 12.7 and 12.9
min; (S)- and (R)-21, 27.7 and 27.9 min; (S)- and (R)-24, 50.1
and 51.9 min. The optical rotation data of the products obtained
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25
in the reduction of 1, 2, 6, and 7 were the following. 17: ½ꢀꢁ
D
1
5
25
D
þ114:9 (c 0.52, CHCl3) {lit. : ½ꢀꢁ ꢂ110:5 for (R)-enantiomer};
2
D
5
25
D
1
8: ½ꢀꢁ þ127:7 (c 0.55, CHCl3); 22: ½ꢀꢁ þ30:2 (c 0.39,
2b
15 25
CHCl3) {lit. : ½ꢀꢁ ꢂ23:7 for (1R,4S)-enantiomer}; 23: ½ꢀꢁ
D
D
2
b
15
ꢂ19:5 (c 0.34, CHCl3) {lit. : ½ꢀꢁ þ13:9 for (1R,4R)-enantio-
D
mer}. The CD data of the products obtained in the reduction of
3 K. Matsumoto, Y. Kawabata, J. Takahashi, Y. Fujita, and
M. Hatanaka, Chem. Lett., 1998, 283.
3
–5 and 8 were the following. 19a converted from 3: ½ꢂꢁ
2
88
16
þ887 (c 0.75, MeOH) {lit. : ½ꢂꢁ
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288
4
(2000).
5
K. Shimoda and T. Hirata, J. Mol. Catal. B: Enzym., 8, 255
2
88
1
0
9a from 12: ½ꢂꢁ þ701 (c 0.68, MeOH); 20: ½ꢂꢁ þ1914 (c
288
17
.32, MeOH) {lit. : ½ꢂꢁ
þ2200}; 21: ½ꢂꢁ
þ1860 (c 0.15,
Y. Kawai, M. Hayashi, and N. Tokitoh, Tetrahedron:
2
88
288
1
7
MeOH) {lit. : ½ꢂꢁ þ2480}; 24: ½ꢂꢁ þ995 (c 0.14, MeOH).
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288
288
The product alcohols produced in the reduction of 3, 11, 12, 15,
and 16 were identified by direct comparisons of TLC, GLC, and
6
6
GC–MS data with those of authentic samples. The absolute con-
figurations and enantiomeric purities of 19b and 19c were deter-
mined by H NMR analyses of the corresponding MTPA esters,
7
1
8
as described previously.18 The absolute configurations of 26b
and 30b after esterification with propionyl chloride and pyridine
in CH2Cl2 were determined by comparing the GLC retention
times on CP cyclodextrin ꢁ 236M-19 column with those of corre-
sponding esters prepared from enantiomerically pure alcohols.
The enantiomeric compositions of 26b and 30b were determined
by the peak areas of their corresponding propionyl esters in the
chiral GLC analyses. Retention times for the esterified enantiom-
ers in the GLC were as follows: (S)- and (R)-sec-butyl propionate,
9 K. Shimoda, S. Izumi, and T. Hirata, Bull. Chem. Soc. Jpn.,
75, 813 (2002).
10 F. Huet, M. Pellet, and J. M. Conia, Tetrahedron Lett., 18,
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11 D. F. Taber, J. Org. Chem., 41, 2649 (1976).
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14 T. Hirata, Y. Tang, K. Okano, and T. Suga, Phytochemis-
try, 28, 3331 (1989).
5
.9 and 6.7 min; (S)- and (R)-1-ethylbutyl propionate, 7.1 and 7.8
min.
Reduction of Ketones with Synechococcus sp. PCC 7942.
Substrate ketones were incubated with Synechococcus sp. PCC
942 for 2 days in a manner similar to that described above.
15 J. J. Partridge, N. K. Chada, and M. R. Vskokovic, J. Am.
Chem. Soc., 95, 532 (1973).
7
The product alcohols were identified by comparisons of their
TLC, GLC, and GC–MS data with those of authentic samples.
The absolute configurations and the enantiomeric compositions
of the products were determined by chiral GLC analyses of their
corresponding acetyl or propionyl esters on CP cyclodextrin ꢁ
16 C. J. Cheer and C. Djerassi, Tetrahedron Lett., 17, 3877
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17 A. I. Meyers, D. R. Williams, G. W. Erickson, S. White,
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Chem. Soc., 108, 162 (1986).
2
36M-19 column. Retention times for the esterified enantiomers
in the GLC were as follows: (S)- and (R)-1-methylbutyl acetate,
.5 and 8.4 min; (S)- and (R)-1-methylpentyl propionate, 7.1
5
and 8.8 min; (S)- and (R)-1-methylhexyl propionate, 6.0 and 6.8
min. The optical rotation data of the products obtained in the re-
20 R. Backstrom and B. Sjoberg, Ark. Kemi, 26, 549 (1967).