Simple preparation of optically pure bis(trifluoromethyl)alkanediols through lipase-catalyzed reaction

Tetrahedron Letters

Volumn 37, Issue 28, 1996, Pages 5001-5002

  Itoh, Toshiyuki ^c   Shiromoto, Mizuho ^a   Inoue, Hitomi ^c   Hamada, Hiroki ^a   Nakamura, Kaoru ^b  

^a OKAYAMA UNIVERSITY OF SCIENCE   (Japan)

^b KYOTO UNIVERSITY   (Japan)

^c OKAYAMA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACETOACETIC ACID; TRIACYLGLYCEROL LIPASE;

ARTICLE; CANDIDA; DRUG HYDROLYSIS; ENANTIOMER; ESTERIFICATION; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; LIQUID CRYSTAL; STEREOCHEMISTRY;

EID: 15844366018     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00994-X     Document Type: Article

References (9)

1. 1) (a) Clark, N. A.; Lagerwal, S. T. Springer Ser. Chem. Phys., 1980, 11(Liq. Cryst. One-and Two-Dimens. Order), 222-227.
2. (b) Skarp, K.; Handschy, M. A. Mol. Cryst. Liq. Cryst., 1988, 165, 439-509.
3. (c) Nohira, H. J. Synth. Org. Chem., Jpn. 1991, 49, 467-474.
4. (d) "Future Liquid Crystal Display and Its Materials," ed. by Fukuda, A., CMC, Tokyo (1992). and references cited therein.
5. A* phase, while liquid crystals prepared from 3 with even number of n exhibited SmC* and SmA phase.
6. 3) Preparation of 96%ee of (trifluoromethyl)oxirane was reported recently through enantioselective reduction of 1,1,1-trifluoro-3-chloro-2-propanone by chlorodisiopinocamphenylborane: Ramachandran, P. V.; Gong, B.; Brown, H. C. J. Org.Chem. 1995, 60, 41-46.
7. 4) Hamada, H.; Shiromoto, M.; Funahashi, M.; Itoh, T.; Nakamura, K. J. Org.Chem. 1996, 61, 2332-2336.
8. 5) CAL has the highest acylation efficiency of 1,1,1-trifluoro-2-alkanols among 25 types of commercial enzymes. For preparing optically active 1,1,1-trifluoro-2-nonanol, the trans-esterification method gave the product with better %ee than hydrolysis of the corresponding acetate in 0.1 M phosphate buffer at pH7.2, though the hydrolysis reaction proceeded more speedily than trans-esterification. See ref. 4. We re-examined CAL-catalyzed hydrolysis of 1,1,1-trifluoro-2-nonyl acetate under the present mixed solvent system, and found that hydrolyzed alcohol formed in an optically pure state with good yield. The mixed solvent system seemed effective to suppress non-enzymatic hydrolysis reaction of the acetate. Therefore, perfect resolution of 1,1,1-trifluoro-2-alkanols was achieved by both hydrolysis-and trans-esterification methods using CAL.
9. (S,S) = 23.1 min. Assignment was carried out by comparing the authentic samples derived from commercial 75%ee of (S)-3,3,3-trifluoro-1,2-epoxypropane. Tetrahedron Letters, Vol. 37, No. 28, pp. 5003-5006, 1996