A Mild Chemo-Enzymatic Oxidation–Hydrocyanation Protocol
FULL PAPER
2
6% yield, 87% ee); R
f
(PE/EA, 95:5) = 0.35. [α]22
). H NMR (250.13 MHz): δ = 1.02 (t, J = 7.4 Hz, 3 H,
CH ), 2.03–2.12 (m, 2 H, CH CH ), 2.15 (s, 3 H, CH C=O),
.56–2.62 (m, 2 H, CH CHCN), 5.30–5.45 (m, 2 H, CH=CH),
.71–5.82 (m, 1 H, CHCN) ppm. 13C NMR (100.61 MHz): δ =
3.2 (CH –CH ), 20.1 (CH C=O), 25.4 (CH –CH ), 35.4 (CH ),
0.9 (CH–O), 116.4 (CN), 119.5 (CH–CH –CH), 139.0 (CH–CH
), 168.9 (C=O) ppm. MS (C N, m/z, relative intensity):
67 [M , 16], 149 (52), 142 (24), 106 (48), 83 (52), 69 (100).
D
= –32 (c = 1,
[13] F. Effenberger, Stereoselective Biocatalysis (Ed.: R. N. Patel),
Marcel Dekker Inc., New York, 2000, p. 321.
1
CHCl
CH
2
5
1
6
3
[
[
[
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2
3
2
3
Opin. Chem. Biol. 2000, 4, 103–109.
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2
3
2
3
3
2
2
2
2
–
CH
1
3
9
H
13
O
2
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+
[
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(2S)-2-(tert-Butyldimethylsilanyloxy)-4-pentenenitrile (5a): A solu-
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[
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tion of recrystallised imidazole (0.87 g, 12.8 mmol) and tert-butyl-
dimethylsilyl chloride (2.11 g, 14 mmol) in 70 mL DMF was stirred
at 0 °C for 20 min. The crude solution of 1a, prepared from 3a
5
[
2
000, 11, 532–539.
(844 mg, 11.7 mmol) according to general procedure B using pH 4
[
[
22] K. Gruber, Proteins 2001, 44, 26–31.
was added, the mixture was warmed to room temp. and stirred
overnight. The reaction mixture was diluted with 70 mL of water
and extracted with diethyl ether (3×110 mL). The combined or-
ganic layers were washed with water (2×100 mL) and then with
brine (1×100 mL). The organic layer was dried with Na SO and
2 4
concentrated under reduced pressure. The crude product was puri-
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1
999, 24, 514–522.
[
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[
[
[
[
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4
769–4772.
fied by column chromatography on silica (PE/EA, 98:2) yielding 5a
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995, 6, 845–848.
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0425.
as a clear oil (659 mg, 37% yield, 95% ee); R
f
(PE/EA, 95:5) =
). H NMR (250 MHz): δ = 0.17 (s,
Si), 0.22 (s, 3 H, CH Si), 0.94 (s, 9 H, tBut), 2.53–2.59
CHCN), 4.47 (t, J = 6.5 Hz, 1 H, CHCN), 5.23–5.30
m, 2 H, CH=CH ), 5.84 (ddt, J = 17.4, 9.8 and 7.0 Hz, 1 H,
) ppm. 13C NMR (62.90 MHz): δ = –4.93 (CH
–Si), –4.73
–Si), 18.49 [Si–C(CH )], 25.90 [Si–C(CH )], 41.11 (CH
O), 62.31 (CH–O), 120.00 (CN), 120.51 (CH
CH =CH) ppm. HRMS (EI) calculated for C11
11.1392 found 211.1409. MS (C11
1
2
1
0
3
.74. [α]2
D 3
= –60 (c = 1, CHCl
H, CH
3
3
1
(
(
m, 2 H, CH
2
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2
CH=CH
CH
2
3
(
3
3
3
2
–CH– [29] T. Wirth, Angew. Chem. Int. Ed. 2005, 44, 3656–3665.
[
[
[
[
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(
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H
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H21NOSi, m/z, relative inten-
7
552.
+
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1
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[
[
[
35] When NaOCl or NaOCl/KBr was used as primary oxidant in
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We thank DSM (M. Wubbolts) for the HbHNL. D. J. V. and L. V.
thank NWO/JC and NWO/ACTS, respectively, for financial sup-
port. U. H. thanks the Royal Netherlands Academy of Arts and
Sciences (KNAW) for a fellowship.
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Received: November 10, 2005
Published Online: January 26, 2006
Eur. J. Org. Chem. 2006, 1672–1677
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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