N. A. Salvi, S. Chattopadhyay / Tetrahedron: Asymmetry 22 (2011) 1512–1515
1515
354; (c) Bornscheuer, U. T.; Kazlauskas, R. J. Hydrolases in Organic Synthesis:
Regio- and Stereoselective Biotransformations, 2 ed.; Wiley-VCH: Weinheim,
2005; (d) van Rantwijk, F.; Sheldon, R. Chem. Rev. 2007, 107, 2757–2785; (e)
Hudlicky, T.; Reed, J. W. Chem. Soc. Rev. 2009, 38, 3117–3132.
3.7. (R)-1-Phenylbutan-2-ol 8b
Yield: 69.6%; ½a D24
ꢂ
¼ ꢃ31:1 (c 2.82, CHCl3), {lit.15e
½
a 2D5
ꢂ
¼ þ21:3
2. (a) Jones, J. B.; Beck, J. F. In Application of Biochemical Systems in Organic
Chemistry. Part 1; Jones, J. B., Sih, C. J., Perlman, D., Eds.; Wiley: New York, 1976;
Vol. X, pp 236–401; (b) Faber, K. Biotransformations in Organic Chemistry, 2nd
ed.; Springer: Berlin, 1995; (c) Roberts, S. M.; Turner, A. J.; Willetts, A. J.; Turner,
M. K. Introduction to Biocatalysis Using Enzymes and Microorganisms; Cambridge
University Press: New York, 1995; (d) Nakamura, K.; Yamanaka, R.; Matsuda,
T.; Harada, T. Tetrahedron: Asymmetry 2003, 14, 2659–2681.
(c 0.65, Et2O) for (S)-8b of 94.9% ee}.
3.8. (R)-1-Phenylhexan-2-ol 10b
Yield: 29.3%; ½a D24
ꢂ
¼ ꢃ17:2 (c 1.18, CHCl3), ½a D24
¼ þ3:9 (c 1.14,
ꢂ
MeOH), {lit.15f
½
a 2D5
ꢂ
¼ þ4:5 (c 0.8, MeOH) for (S)-10b of 94% ee}.
3. (a) Poppe, I.; Novak, I. Selective Biocatalyst
a Synthetic Approach; VCH,
Verlagsgsellschaff mbH: Weinhein, 1992; (b) Turner, N. J. Chem. Ind. (London)
1994, 592–595.
4. (a) Shieh, W.-R.; Gopalan, A. S.; Sih, C. J. J. Am. Chem. Soc. 1985, 107, 2993–2994;
(b) Nakamura, K.; Kawai, Y.; Nakajima, N.; Ohno, A. J. Org. Chem. 1991, 56,
4778–4783; (c) Nakamura, K.; Kondo, S.; Kawai, Y.; Nakajima, N.; Ohno, A.
Biosci., Biotechnol., Biochem. 1994, 58, 2236–2240.
5. (a) Nakamura, K.; Inoue, Y.; Matsuda, T.; Ohno, A. Tetrahedron Lett. 1995, 36,
6263–6266; (b) Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901–
2913; (c) Strauss, U. T.; Felfer, U.; Faber, K. Tetrahedron: Asymmetry 1999, 10,
107–117; (d) Azerad, R.; Buisson, D. Curr. Opin. Biotechnol. 2000, 11, 565–571;
(e) Nakamura, K.; Fujii, M.; Ida, Y. Tetrahedron: Asymmetry 2001, 12, 3147–
3153; (f) Voss, C. V.; Gruber, C. C.; Faber, K.; Knaus, T.; Macheroux, P.; Kroutil,
W. J. Am. Chem. Soc. 2008, 130, 13969–13972; (g) Voss, C. V.; Gruber, C. C.;
Kroutil, W. Angew. Chem., Int. Ed. 2008, 47, 741–745.
3.9. (S)-4-Phenylbutan-2-ol 11b
Yield: 81.9%; ½a D24
ꢂ
¼ þ15:3 (c 3.32, CHCl3), {lit.15f
½
a 2D5
ꢂ
¼ þ12:3
(c 1.0, CHCl3), >93% ee}.
3.10. (S)-4-(40-Methoxyphenyl)butan-2-ol 12b
Yield: 75.9%; ½a D24
¼ þ13:1 (c 3.07, CHCl3). Anal. Calcd for
ꢂ
C11H16O2: C, 73.30; H, 8.95. Found: C, 73.34; H, 9.17.
6. (a) Nakamura, K.; Matsuda, T. J. Org. Chem. 1998, 63, 8957–8964; (b) Nakamura,
K.; Inoue, Y.; Matsuda, T.; Misawa, I. J. Chem. Soc., Perkin Trans. 1 1999, 2397–
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43, 3629–3631.
7. (a) Zhou, B. N.; Gopalan, A. S.; VanMiddlesworth, F.; Ru Shieh, W.; Sih, C. J. J. Am.
Chem. Soc. 1983, 105, 5925–5926; (b) Manzocchi, A.; Fiecchi, A.; Santaniello, E.
J. Org. Chem. 1988, 53, 4405–4407. and references cited therein.
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1085; (b) Ziffer, H.; Kawai, K.; Kasai, M.; Imuta, M.; Froussios, C. J. Org. Chem.
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2833–2839; (d) Salvi, N. A.; Badheka, L. P.; Chattopadhyay, S. Biotechnol. Lett.
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Asymmetry 2004, 15, 3397–3400; (f) Salvi, N. A.; Chattopadhyay, S. Bioorg.
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3.11. (S)-1-Phenoxypropan-2-ol 13b
Yield: 75.5%; ½a D24
ꢂ
¼ þ25:2 (c 3.06, CHCl3), {lit.15h
½
a 2D5
ꢂ
¼ ꢃ2:7 (c
1.8, EtOH); >99% ee (R)-13b}.
3.12. (S)-1-(40-Chlorophenylthio)propan-2-ol 14b
Yield: 29.2%; ½a D24
¼ þ41:9 (c 1.18, CHCl3). Anal. Calcd for
ꢂ
C9H11ClOS: C, 53.33; H, 5.47; Cl, 17.49; S, 15.82. Found: C, 53.47;
H, 5.59; Cl, 17.71; S, 15.59.
3.13. General procedure for preparation of the MTPA esters
To a stirred solution of the alcohol (15 mg), pyridine (0.1 mL),
and 4,4-dimethylaminopyridine (1–2 crystals) in CH2Cl2 (0.5 mL)
was injected (R)-MTPA chloride (25 mg) in CH2Cl2 (0.5 mL). After
stirring the mixture for 16 h at room temperature, the excess pyr-
idine was removed by purging with N2 gas, and the residue sub-
jected to preparative thin-layer chromatography (silica gel, 10%
EtOAc/hexane) to isolate the respective MTPA esters. The 1H
NMR analyses were carried out with the pure samples. The MTPA
esters of the racemic alcohols were also prepared as above and
the diagnostic 1H NMR methoxyl resonances for them were as fol-
lows: 3b. 1H NMR: d 3.37 and 3.50; 5b. 1H NMR: d 3.40 and 3.49;
6b. 1H NMR: d 3.40 and 3.48; 8b. 1H NMR: d 3.40 and 3.49; 10b.
1H NMR: d 3.39 and 3.48; 11b. 1H NMR: d 3.46 and 3.59; 12b. 1H
NMR: d 3.45 and 3.59; 13b. 1H NMR: d 3.46 and 3.56; 14b. 1H
NMR: d 3.45 and 3.55.
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Acknowledgment
N.A.S. thanks Ms. Gincy Marina Mathew, a project trainee,
Department of Biotechnology, Karpagam Arts & Science College,
Coimbatore for her assistance.
References
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