Kinetic resolution of racemic 2-substituted 3-cyclopenten-1-ols by lipase-catalyzed transesterifications: A rational strategy to improve enantioselectivity

Tadashi Ema, Soichi Maeno, Yusuke Takaya, Takashi Sakai, Masanori Utaka

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Abstract

The effect of the acyl group of acylating agents on the enantioselectivity in the Pseudomonas cepacia lipase-catalyzed acylations of racemic alcohols has been studied. 2-[(N,N-Dimethylcarbamoyl)-methyl]-3-cyclopenten-1-ol (1) and 2-[2-(tert-butyldimethylsilyloxy)ethyl]-3-cyclopenten-1-ol (4) were resolved with a variety of enantioselectivities. In the case of alcohol 1, the enantiomeric ratio (the E value) was increased by changing the acylating agent from vinyl acetate (E = 30) to vinyl butyrate (E = 156) and dropped substantially with longer acyl donors. With vinyl chloroacetate, the reaction rate was fast and the enantioselectivity was high (E = 89), whereas the resolution with vinyl trifluoroacetate resulted in a very poor enantioselectivity (E = 4). The bulky acylating agent, vinyl pivalate, gave a moderate enantioselectivity (E = 15). In the case of alcohol 4, the enantioselectivities were excellent (E > 142) except vinyl pivalate (E = 12). It is indicated that the acyl group transiently attached at the active site of the lipase acts as a stereochemical controller. The solvent effect is also described briefly. A clear correlation was observed between the E values and the log P values of the organic solvents; the smaller the log P value of the solvent, the higher the E value.

Original languageEnglish
Pages (from-to)8610-8616
Number of pages7
JournalJournal of Organic Chemistry
Volume61
Issue number24
DOIs
Publication statusPublished - Nov 29 1996

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Enantioselectivity
Transesterification
Lipase
Kinetics
Alcohols
Acylation
Organic solvents
Reaction rates
Controllers

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Kinetic resolution of racemic 2-substituted 3-cyclopenten-1-ols by lipase-catalyzed transesterifications : A rational strategy to improve enantioselectivity. / Ema, Tadashi; Maeno, Soichi; Takaya, Yusuke; Sakai, Takashi; Utaka, Masanori.

In: Journal of Organic Chemistry, Vol. 61, No. 24, 29.11.1996, p. 8610-8616.

Research output: Contribution to journalArticle

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