Preparation of optically active allylic hydroperoxy alcohols and 1, 3-diols by enzyme-catalyzed kinetic resolution and photooxygenation of chiral homoallylic alcohols.
All four possible enantiomers of the 3-hydroperoxy-4-penten-1-ols 2a, b and their corresponding 4-pentene-1,3-diols 4a,b have been prepared for the first time in high enantiomeric purity (up to 98% ee) and in preparative amounts according to two distinct ways: First the photooxygenation of the racemic homoallylic alcohols 1 gave the racemic hydroperoxy alcohols 2, which have subsequently been kinetically resolved by horseradish peroxidase (HRP); alternatively, first the lipase-catalyzed resolution afforded the optically active homoallylic alcohols 1 and subsequent photooxygenation led to the enantiomerically enriched hydroperoxy alcohols 2.
Adam
W
W
Institute of Organic Chemistry, University of Würzburg, Am Hubland, 97074 Würzburg, Germany. adam@chemie.uni-wuerzberg.de
Saha-Möller
C R
CR
Schmid
K S
KS
D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism; D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism; D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism; D002384:Catalysis; D006735:Horseradish Peroxidase / Q000378:metabolism*; D006861:Hydrogen Peroxide / Q000737:chemistry* / Q000378:metabolism; D007700:Kinetics; D008027:Light; D008049:Lipase / Q000378:metabolism; D010084:Oxidation-Reduction; D010100:Oxygen / Q000378:metabolism; D010777:Photochemistry; D013237:Stereoisomerism
D000438:Alcohols; D000475:Alkenes; D000498:Allyl Compounds; D006861:Hydrogen Peroxide; D006735:Horseradish Peroxidase; D008049:Lipase; D010100:Oxygen