111423-27-9Relevant articles and documents
Different stereochemistry for the reduction of trifluoromethyl ketones and methyl ketones catalyzed by alcohol dehydrogenase from Geotrichum
Nakamura, Kaoru,Matsuda, Tomoko,Itoh, Toshiyuki,Ohno, Atsuyoshi
, p. 5727 - 5730 (1996)
Reduction of trifluoromethyl ketones by a crude alcohol dehydrogenase from Geotrichum affords (S)-trifluoromethyl carbinols in excellent ee, whereas the reduction of methyl ketones gives the corresponding alcohols of the opposite configuration in excellent ee.
Two Classes of Enzymes of Opposite Stereochemistry in an Organism: One for Fluorinated and Another for Nonfluorinated Substrates
Matsuda, Tomoko,Harada, Tadao,Nakajima, Nobuyoshi,Itoh, Toshiyuki,Nakamura, Kaoru
, p. 157 - 163 (2007/10/03)
Reduction of methyl ketones by dried cells of Geotrichum candidum (APG4) afforded (S)-alcohols in excellent enantiomeric excess (ee), whereas the reduction of trifluoromethyl ketones gave the corresponding alcohols of the opposite configuration also in excellent ee. The replacement of the methyl moiety with a trifluoromethyl group alters both the bulkiness and the electronic properties, the effect of which on the stereoselectivity was examined. No inversion in stereochemistry was observed in the reduction of hindered ketones such as isopropyl ketone, while the stereoselectivity was inverted in the reduction of ketones with electron-withdrawing atoms such as chlorine. The mechanism for the inversion in stereochemistry was investigated by enzymatic studies. Several enzymes with different stereoselectivities were isolated; one of them catalyzed the reduction of methyl ketones, and another with the opposite stereoselectivity catalyzed the reduction of trifluoromethyl ketones. Furthermore, both APG4 and the isolated enzyme were applied to the reduction of fluorinated ketones on a preparative scale, which resulted in the synthesis of chiral fluorinated alcohols with excellent ee.
Efficient synthesis of optically pure 1,1,1-trifluoro-2-alkanols through lipase-catalyzed acylation in organic media
Hamada, Hiroki,Shiromoto, Mizuho,Funahashi, Makoto,Itoh, Toshiyuki,Nakamura, Kaoru
, p. 2332 - 2336 (2007/10/03)
Lipase-catalyzed esterification was successfully utilized for the optical resolution of 1,1,1-trifluoro-2-alkanol 1 when racemic 1 was treated with lipase from Candida antarctica in hexane in the presence of molecular sieves (4 A) to provide the corresponding (S)-acetate 2 in an optically pure state. Alkanol 1 is known as an important component of liquid crystal compounds which display remarkable ferroelectric liquid crystal (FLC) characteristics. Five types of optically pure alkanols, i.e., 1,1,1-trifluoro-2-octanol (1a), 1,1,1-trifluoro-2-nonanol (1b), 1,1,1-trifluoro-2-decanol (1c), 1,1,1-trifluoro-2-undecanol (1d), and 1,1,1-trifluoro-8-(benzyloxy)-2-octanol (1e), were thus obtained by the lipase-catalyzed acylation.