Efficient lipase-catalyzed enantioselective desymmetrization of prochiral 2,2-disubstituted 1,3-propanediols and meso 1,2-diols using 1-ethoxyvinyl 2-furoate.

Shuji Akai, Tadaatsu Naka, Tetsuya Fujita, Yasushi Takebe, Toshiaki Tsujino, Yasuyuki Kita

Graduate School of Pharmaceutical Sciences, Osaka University, Yamada-oka, Suita, Osaka 565-0871, Japan.

The Journal of organic chemistry 2002 Jan 25

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An efficient lipase-catalyzed desymmetrization of prochiral 2,2-disubstituted 1,3-propanediols was developed using 1-ethoxyvinyl 2-furoate 1b, for which the well-known method using vinyl or isopropenyl acetate has had limited success due to low reactivity and easy racemization of the products through acyl group migration. The reagent 1b is highly reactive and converts various prochiral 1,3-diols to the monoesters having a chiral quaternary carbon center with 82-99% ee. These products were stable against racemization under acidic conditions, and their furoyl groups were compatible with oxidative conditions. Prolonging the reaction time led to the kinetic resolution of the monoesters resulting in an increase of their optical purity. The similar desymmetrization of meso cis-1,2-cycloalkanediols gave the monoesters with 82-97% ee without racemization.

Citation

Shuji Akai, Tadaatsu Naka, Tetsuya Fujita, Yasushi Takebe, Toshiaki Tsujino, Yasuyuki Kita. Efficient lipase-catalyzed enantioselective desymmetrization of prochiral 2,2-disubstituted 1,3-propanediols and meso 1,2-diols using 1-ethoxyvinyl 2-furoate. The Journal of organic chemistry. 2002 Jan 25;67(2):411-9