Facile Preparation of Optically Active Bicyclo[3.3.1]nonane-2,6-diol and 3,3,7,7-Tetramethylbicyclo[3.3.1]nonane-2,6-diol by Enzyme-Catalyzed Hydrolysis, and Enantiomer Recognition Behavior of Crown Ethers and Podands Having These Diols as a Chiral Subunit

Abstract

Abstract Hydrolysis of 2,6-diacetoxybicyclo[3.3.1]nonane (5) using lipase from Candida cylindracea gave (+)-(1S,2R,5S,6R)-6-acetoxybicyclo[3.3.1]nonan-2-ol (4) with 81% e.e. and (−)-(1R,2S,5R,6S)-5 with 95% e.e., and pig liver esterase-catalyzed hydrolysis of 2,6-diacetoxy-3,3,7,7-tetramethylbicyclo[3.3.1]nonane (9) afforded (−)-(1S,2R,5S,6R)-3,3,7,7-tetramethylbicyclo[3.3.1]nonane-2,6-diol (7) with 96% e.e. and (+)-(1R,2S,5R,6S)-9 with 86% e.e. By lithium aluminum hydride reduction, (+)-4 and (−)-5 were converted to (+)-bicyclo[3.3.1]nonane-2,6-diol (3) and (−)-3 with high optical purity, respectively, and (+)-7 was obtained from (+)-9. Using these optically active diols 3 and 7 as a chiral subunit, optically active crown ethers and podands were prepared and their enantiomer recognition behavior was evaluated by the enantiomer differential transport of (±)-1,2-diphenylethylamine and methyl ester of (±)-phenylglycin hydrochloride through bulk liquid membrane.