Enzymatic resolution, desymmetrization, and dynamic kinetic asymmetric transformation of 1,3-cycloalkanediols.
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.
Fransson
Ann-Britt L
AB
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm, Sweden.
Xu
Yongmei
Y
Leijondahl
Karin
K
Bäckvall
Jan-E
JE
D000080:Acetals / Q000737:chemistry; D000085:Acetates / Q000737:chemistry; D000215:Acylation; D000473:Alkanes / Q000737:chemistry* / Q000378:metabolism*; D002176:Candida albicans / Q000201:enzymology; D002384:Catalysis; D003500:Cyclization; D005656:Fungal Proteins; D007700:Kinetics; D008049:Lipase / Q000378:metabolism*; D015394:Molecular Structure; D013237:Stereoisomerism
D000080:Acetals; D000085:Acetates; D000473:Alkanes; D005656:Fungal Proteins; D008049:Lipase; C431349:lipase B, Candida antarctica