Enzymatic Resolution, Desymmetrization and Dynamic Kinetic Asym-metric Transformation of 1,3-Cycloalkanediols
Stockholm University, Faculty of Science, Department of Organic Chemistry2006 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 71, no 17, 6309-6316 p.Article in journal (Refereed) Published
An efficient desymmetrization of cis-1,3-cyclohexanediol to (1S,3R)-3-(acetoxy)-1-cyclohexanol ((R,S)-2a) was performed via Candida antarctica lipase B (CALB)-catalyzed transesterification, in high yield (up to 93%) and excellent enantioselectivity (ee's up to >99.5%). (R,R)-Diacetate ((R,R)-3a) was obtained in a DYKAT process at room temperature from (1S,3R)-3-acetoxy-1-cyclohexanol ((R,S)-2a), in a high trans/cis ratio (91:9) and in excellent enantioselectivity of >99%. Metal- and enzyme-catalyzed dynamic transformation of cis/trans-1,3-cyclohexanediol using PS-C gave a high diastereoselectivity for cis-diacetate (cis/trans = 97:3). The (1R,3S)-3-acetoxy-1-cyclohexanol (ent-(R,S)-2a) was obtained from cis-diacetate by CALB-catalyzed hydrolysis in an excellent yield (97%) and selectivity (>99% ee). By deuterium labeling it was shown that intramolecular acyl migration does not occur in the transformation of cis-monoacetate to the cis-diacetate.
Place, publisher, year, edition, pages
American Chemical Society , 2006. Vol. 71, no 17, 6309-6316 p.
IdentifiersURN: urn:nbn:se:su:diva-25248DOI: 10.1021/jo060002nOAI: oai:DiVA.org:su-25248DiVA: diva2:199232
Part of urn:nbn:se:su:diva-7892006-01-042006-01-042010-09-14Bibliographically approved