´
A. Solıs et al. / Tetrahedron 60 (2004) 10427–10431
10431
4. Experimental
2.08 (m, 2H), 3.72 (br, 1H), 4.94 (d, JZ6.4 Hz, 1H), 5.59
(dd, JZ15.5, 6.4 Hz, 1H), 6.03 (m, 1H).
4.1. Chemicals and sources of enzymes
4.2.5. (R)-(K)-2-Hydroxy-3E,5E-heptadienenitrile (2e).
Conversion 79%, [a]2D2ZK52 (c 3.85, CH2Cl2) ee 69%;
lit.:18 [a]2D3ZK24.9 (c 1, CHCl3), ee 96%. 1H NMR
(CDCl3): dZ1.8 (d, JZ6.45 Hz, 3H), 3.87 (br, 1H), 4.99 (d,
JZ6.0 Hz, 1H), 5.62 (dd, JZ15.2, 6.0 Hz, 1H), 5.91 (m,
1H), 6.06 (dd, JZ15.0, 10.4 Hz, 1H), 6.46 (dd, JZ15.0,
10.4 Hz, 1H).
Ripe mamey (Pouteria sapota) seeds were obtained from a
fresh fruit purchased in a local grocery store. The mamey
seeds were ground and washed three times with acetone and
once with diisopropyl ether, after filtration by suction the
powder was air dried and stored at 4 8C. Commercial
aldehydes were purchased from Aldrich.
Optical rotations were measured in a Perkin–Elmer
polarimeter model 341. Enantiomeric excesses were
determined by HPLC analyses, using a Chiracel OD column
using hexanes–isopropanol as eluent in a Hewlett–Packard
1050 series, equipped with a diode array detector. Conver-
sion percentages were determined by NMR. 1H NMR
spectra were recorded on a Varian at 400 MHz using CDCl3
as a solvent and TMS as internal reference.
Acknowledgements
We thank the financial support of Consejo Nacional de
´ ´
Ciencia y Tecnologıa (CONACyT), Mexico, Grant Num.
37272-N.
4.2. General procedure for enzymatic reactions
References and notes
HCN (1.5 equiv) was extracted from a buffer solution
(KCN/citric acid, 1 M, pH 5.0) with the proper solvent (2!
2.5 mL). To this solution was added the citrate buffer
solution (0.1 M, pH 5.0); the quantity added to the reaction
medium depended on the experiment, then 200 mg of
mamey defatted meal were added and stirred for 10 min at
room temperature, after this 1 mmol of the aldehyde was
added. The reaction mixture was stirred for the necessary
time at 4 8C, filtered, dried over sodium sulfate and the
solvent was evaporated to dryness. Enantiomeric excess was
determined by HPLC using a Chiracel OD column with
hexanes–isopropyl alcohol as eluent and conversion per-
centage was determined by 1H NMR, of the crude product.
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8. Solıs, A.; Luna, H.; Perez, H. I.; Manjarrez, N. Tetrahedron:
4.2.1. (R)-(C)-2-Hydroxy-4-phenyl-3E-butenenitrile
(2a). Conversion 54%, [a]2D2ZC17 (c 1, CH2Cl2), ee
1
72%; lit.:12 [a]D13ZC26.1 (c 0.78, CHCl3), ee 69.3%. H
´
´
NMR (CDCl3): dZ5.18 (d, JZ6.0 Hz, 1H), 6.26 (dd, JZ
16.0, 6.0 Hz, 1H), 6.9 (d, JZ6.0 Hz, 1H), 7.35 (m, 5H).
Asymmetry 2003, 14, 2351–2353.
9. Klempier, N.; Pichler, U.; Griengl, H. Tetrahedron: Asym-
metry 1995, 6, 848–854.
4.2.2. (R)-(C)-2-Hydroxybenzeneacetonitrile (2b). Con-
version 95%, [a]D22ZC46 (c 1.9, CH2Cl2); lit.:12 [a]D20Z
C47.5 (c 1.89, CHCl3), ee O99%. H NMR (CDCl3):
10. (a) Peterson, C. J.; Tsao, R.; Coats, J. R. Pest. Manag. Sci.
2000, 56, 615–617. (b) Peterson, C. J.; Tsao, R.; Eggler,
A. L.; Coats, J. R. Molecules 2000, 5, 648–654.
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349–354.
1
dZ5.52 (s, 1H), 7.49 (m, 5H).
4.2.3. (R)-(K)-2-Hydroxy-3-methyl-3E-hexanenitrile
(2c). Conversion 84%, [a]2D2ZK72 (c 3.9, CH2Cl2), ee
89%. 1H NMR (CDCl3): dZ1.0 (t, JZ7.6 Hz, 3H), 1.78 (s,
3H), 2.09 (m, 2H), 3.42 (br, 1H), 4.83 (s, 1H), 5.72 (t, JZ
7.6 Hz, 1H). Configuration was assigned on the basis of
mamey meal selectivity, and of elution order of the
enantiomers on chiracel OD column using hexanes–
ispropanol (95:5) as eluent, (R)-enantiomer trZ11.37 min,
(S)-enantiomer trZ11.036 min.
12. Lin, G.; Shiqing, H.; Li, Z. Tetrahedron 1999, 55, 3531–3540.
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1105–1116.
14. Han, S.; Lin, G.; Li, Z. Tetrahedron: Asymmetry 1998, 9,
1835–1838.
15. Willeman, W. F.; Straathof, A. J. J.; Heijnen, J. J. Enzyme
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¨
16. Willeman, W. F.; Neuhofer, R.; Wirth, I.; Pochlauer, P.;
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4.2.4. (R)-(K)-2-Hydroxy-3E-heptanenitrile (2d). Con-
version 88%, [a]D22ZK60 (c 3.16, CH2Cl2), ee 95%; lit.:9
17. Rotcenkovs, G.; Kanerva, L. T. J. Mol. Catal. B: Enzym. 2000,
11, 37–43.
1
[a]2D0ZC20.3 (c 0.3, CHCl3), (S)-enantiomer, ee 95%. H
18. Gerrits, P. J.; Zumbragel, F.; Marcus, J. Tetrahedron 2001, 57,
8649–8698.
NMR (CDCl3): dZ0.92 (t, JZ7.6 Hz, 3H), 1.43 (m, 2H),