Enantioselective Benzylic Hydroxylation with Pseudomonas monteilii TA-5
COMMUNICATIONS
(
0.2 mL) were taken at predetermined time points, cells References
were removed by centrifugation, products were extracted
with 1.0 mL ethyl acetate containing 1 mM benzyl alcohol as
internal standard, and organic phase was analyzed.
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Analytical Methods
The concentration and ee values of the bioproducts were de-
termined using a Shimadzu
Daicel
4
TM
Prominence HPLC with a
[
[
[
3] R. Volpini, S. Costanzi, C. Lambertucci, S. Taffi, S. Vit-
TM
OB-H, OD-H, or AS-H chiral column (250ꢂ
.6 mm, 5 mm) at 258C with a flow rate of 1 mLmin and
tori, K. N. Klotz, G. Cristalli, J. Med. Chem. 2002, 45,
À1
3
271–3279.
UV detection at 210 nm. Retention times: 11.7 min for (R)-
4] X. Jiang, Y. K. Lim, B. J. Zhang, E. A. Opsitnick, M. H.
5
and 15.6 min for (S)-5 (OB-H column, 15% i-PrOH:85%
Baik, D. Lee, J. Am. Chem. Soc. 2008, 130, 16812–
n-hexane); 6.3 min for (R)-6 and 7.2 min for (S)-6 (OD-H
column, 10% i-PrOH:90% n-hexane); 10.6 min for (R)-7
and 12.5 min for (S)-7 (AS-H column, 15% i-PrOH:85% n-
hexane); 17.1 min for (R)-8 and 16.0 min for (S)-8 (OD-H
column, 10% i-PrOH:90% n-hexane); 11.8 min for (R)-23
and 14.1 min for (S)-23 (OD-H column, 10% i-PrOH:90%
1
6822.
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b) M. O. Frederick, R. P. Hsung, R. H. Lambeth, J. A.
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n-hexane); 11.1 min for (R)-24 and 12.0 min for (S)-24 (OD-
H
5
1
products were assigned by using authentic samples of (R)-5
and 6, (R)-23–25 as standards in chiral HPLC analyses, and
the configurations of bioproducts (R)-7 and (R)-8 were es-
À1
column, 1.0 mLmin , 5% i-PrOH:95% n-hexane);
.9 min for (R)-25 and 10.1 min for (S)-25 (OD-H column,
0% i-PrOH:90% n-hexane). The configurations of the bio-
2
424; f) S. Morikawa, S. Yamazaki, M. Tsukada, S. Izu-
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[13,18]
7
tablished by comparison with the literature data.
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Preparation of (R)-1-Phenyl-2-propyn-1-ol (5) and
R)-1-Phenyl-2-propen-1-ol (6) by Biohydroxylation
(
[
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The cells of P. monteilii TA-5 were resuspended in 50 mL
0 mM KH PO -K HPO buffer (pH 7.0) containing 10%
5
2
4
2
4
methanol to a density of 6 g cdw/L. Substrate 1 (23.2 mg,
.2 mmol) was added, and the mixture was shaken at 308C
and 300 rpm for 7 h. Similarly, substrate 2 (107.3 mg,
.8 mmol) was added in the same reaction system with a cell
0
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density of 8 g cdw/L and reacted for 7 h. The products (R)-5
and (R)-6 were extracted with ethyl acetate, dried over
MgSO and concentrated by evaporation at reduced pres-
sure, respectively. The crude products (R)-5 and (R)-6 were
purified by flash chromatography (10% EtOAc:90% n-
hexane, R =0.2 for 5 or 6). This gave 17.5 mg of (R)-5 in
[
6
4
2008, 10, 3433–3436; c) G. X. Zhu, X. Y. Lu, Tetrahe-
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f
5
93; b) P. R. Chopade, T. A. Davis, E. Prasad, R. A.
9
5
4% ee and 66% yield and 60.0 mg of (R)-6 in 94% ee and
6% yield, respectively. The purities of (R)-5 and (R)-6
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were both>99% (GC analysis).
1
(
R)-5: H NMR (DMSO, 500 Hz): d=7.599–7.276 (m,
5
H, Ph), 6.026 (d, 1H, CH), 5.351 (s, 1H, CH), 3.471 (s, 1H,
+
OH); MS (GC-MS): m/z=131 (M ).
[
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(
R)-6: H NMR (DMSO, 500 Hz): d=7.367–7.243(m, 5H,
2
006, 8, 4429–4431; b) D. Zhu, H. Ankati, C. Mukher-
Ph), 5.966 (m, 1H, -CH=CH ), 5.459 (d, 1H, -CH-OH),
5
m/z=133 (M ).
2
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2561–2563; c) P. N. Liu, P. M. Gu, F. Wang, Y. Q. Tu,
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.227 (d, 1H, OH), 5.066 (m, 2H, -CH=CH ); MS (GC-MS):
2
+
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Acknowledgements
4
3, 8043–8045.
This work was supported by Science & Engineering Research
Council of A*STAR, Singapore, through a research grant
[16] a) E. N. Kadnikova, V. A. Thakor, Tetrahedron: Asym-
ˇ
(
project No. 0621010024).
metry 2008, 19, 1053–1058; b) J. Stambask y` , A. V.
Adv. Synth. Catal. 2009, 351, 2107 – 2112
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2111