C. Rodríguez et al. / Tetrahedron: Asymmetry 20 (2009) 1168–1173
1173
(CH), 128.3 (2CH), 140.9 (C), 173.7 (C@O). MS (ESI+): m/z (%) 229
References
(100) [M+Na+]. ½a D25
¼ þ35:8 (c 0.91, CHCl3), ee 96%.
ꢄ
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4.4.10. (R)-4-Phenyloctan-3-one, (R)-14a
Yellow pale oil. IR (KBr):
m
3055, 2987, 1719, 1662, 1423 cmꢁ1
.
3
1H NMR (CDCl3, 300.13 MHz): d 0.89 (t, JHH = 7.0 Hz, 3H), 1.00 (t,
3JHH = 7.6 Hz, 3H), 1.16–1.21 (m, 2H), 1.22–1.37 (m, 2H), 1.69–
1.83 (m, 1H), 2.02–2.14 (m, 1H), 2.38–2.49 (m, 2H), 3.66 (t,
3JHH = 7.4 Hz, 1H), 7.24–7.36 (m, 5H). 13C NMR (CDCl3, 75.5 MHz):
d 13.8 (CH3), 13.8 (CH3), 22.5 (CH2), 29.7 (CH2), 31.9 (CH2), 35.0
(CH2), 58.7 (CH), 126.9 (CH), 128.2 (2 CH), 128.7 (2CH), 139.4 (C),
211.3 (C@O). MS (EI+): m/z (%) 204 (1) [M+], 148 (20), 91 (100).
4.4.11. (S)-1-Phenylpentyl propionate, (S)-14b
Yellow pale oil. IR (KBr):
m
3055, 2986, 1731, 1423 cmꢁ1
.
1H
3
NMR (CDCl3, 300.13 MHz): d 0.81 (t, JHH = 7.0 Hz, 3H), 1.10 (t,
3JHH = 6.6 Hz, 3H), 1.20–1.28 (m, 4H), 1.64–1.76 (m, 1H), 1.78–
3
1.90 (m, 1H), 2.24–2.33 (m, 2H), 5.67 (t, JHH = 6.3 Hz, 1H), 7.19–
7.28 (m, 5H). 13C NMR (CDCl3, 75.5 MHz): d 9.0 (CH3), 13.9 (CH3),
22.4 (CH2), 27.6 (CH2), 27.8 (CH2), 36.0 (CH2), 75.8 (CH), 126.4
(2CH), 127.6 (CH), 128.3 (2CH), 140.9 (C), 169.8 (C@O). MS (EI+):
m/z (%) 220 (5) [M+], 164 (28), 117 (100), 91 (55). ½a 2D5
¼ þ21:2
ꢄ
(c 0.58, CHCl3), ee 95%.
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4.4.12. (R)-4-Phenylhept-6-en-3-one, (R)-15a
Yellow pale oil. IR (KBr):
m 3415, 3054, 2983, 1712, 1614,
1494 cmꢁ1
.
1H NMR (CDCl3, 300.13 MHz): d 1.00 (t, JHH = 7.3 Hz,
3
3
3H), 2.35–2.53 (m, 3H), 2.80–2.90 (m, 1H), 3.76 (t, JHH = 7.5 Hz,
1H), 4.97–5.09 (m, 2H), 5.64–5.78 (m, 1H), 7.23–7.30 (m, 5H). 13C
NMR (CDCl3, 75.5 MHz): d 7.7 (CH3), 35.1 (CH2), 36.4 (CH2), 58.4
(CH), 116.5 (CH2), 127.2 (CH), 128.2 (2CH), 128.8 (2CH), 135.8
(CH), 138.6 (C), 210.3 (C@O). MS (APCI+): m/z (%) 189 (100)
9. Torres Pazmiño, D. E.; Snajdrova, R.; Rial, D. V.; Mihovilovic, M. D.; Fraaije, M.
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[M+H+], 227 (8) [M+K]+. ½a 2D5
¼ ꢁ7:2 (c 0.85, CHCl3), ee 38%.
ꢄ
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4.4.13. (S)-4-Phenylbut-1-enyl propionate, (S)-15b
Yellow pale oil. IR (KBr): 3425, 3053, 2984, 1736, 1642,
1494 cmꢁ1 1H NMR (CDCl3, 300.13 MHz): d 1.18 (t, JHH = 7.5 Hz,
m
3
.
3H), 2.36–2.45 (m, 2H), 2.56–2.75 (m, 2H), 5.08–5.15 (m, 2H),
5.65–5.74 (m, 1H), 5.77–5.91 (m, 1H), 7.25–7.43 (m, 5H). 13C–
NMR (CDCl3, 75.5 MHz): d 9.3 (CH3), 28.1 (CH2), 41.1 (CH2), 75.1
(CH), 118.2 (CH2), 126.7 (2CH), 128.1 (CH), 128.6 (2CH), 133.6
(CH), 140.5 (C), 173.9 (C@O). MS (APCI+): m/z (%) 227 (17)
[M+Na+]. ½a 2D5
¼ þ16:9 (c 0.65, CHCl3), ee 77%.
ꢄ
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4.5. Determination of the kinetic parameters
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For the determination of the steady-kinetic parameters of wt
PAMO, M446G PAMO and HAPMO with ketones ( )-1–10a, the
enzymatic activity was determined by monitoring NADPH con-
sumption at 340 nm (e
340 = 6.22 mMꢁ1 cmꢁ1). Stocks solutions of
substrates (1.0 M) were made in dimethyl sulfoxide. A reaction
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mixture (1.0 mL) usually contained 50 mM Tris/HCl (pH 7.5),
100 lM NADPH, 1% (v/v) DMSO and 0.05 lM BVMO. The presence
of 1% DMSO resulted in only a slight decrease in BVMO activity,
while a higher solubility of certain compounds can be achieved.
Acknowledgements
C.R. thanks the Principado de Asturias for her predoctoral fel-
lowship. Dr. G. de G. thanks Ministerio Ciencia e Innovación (MIC-
INN) for personal funding (Juan de la Cierva Program). M.W.F. and
D.E.T.P. are supported by the EU-FP7 ‘Oxygreen’ project. This work
was supported by the MICINN (Project CTQ2007-61126).
18. Bouquillon, S.; Ganchegui, B.; Estrine, B.; Hénin, F.; Muzart, J. J. Organomet.
Chem. 2001, 634, 153–156.
19. Berthiol, F.; Doucet, H.; Santelli, M. Tetrahedron 2006, 62, 4372–4383.