title: Enantioselective route to ketones and lactones from exocyclic allylic alcohols via metal and enzyme catalysis.
abstract: A general and efficient route for the synthesis of enantiomerically pure α-substituted ketones and the corresponding lactones has been developed. Ruthenium- and enzyme-catalyzed dynamic kinetic resolution (DKR) with a subsequent Cu-catalyzed α-allylic substitution are the key steps of the route. The α-substituted ketones were obtained in high yields and with excellent enantiomeric excess. The methodology was applied to the synthesis of a naturally occurring caprolactone, (R)-10-methyl-6-undecanolide, via a subsequent Baeyer-Villiger oxidation.
authors.affiliation: Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm, Sweden.
authors.forename: Madeleine C
authors.initials: MC
authors.lastname: Warner
authors.forename: Anuja
authors.initials: A
authors.lastname: Nagendiran
authors.forename: Krisztián
authors.initials: K
authors.lastname: Bogár
authors.forename: Jan-E
authors.initials: JE
authors.lastname: Bäckvall
mesh_terms: D055162:Biocatalysis; D002175:Candida / Q000201:enzymology*; D003300:Copper / Q000737:chemistry*; D003500:Cyclization; D005656:Fungal Proteins / Q000378:metabolism*; D007659:Ketones / Q000737:chemistry* / Q000378:metabolism; D007783:Lactones / Q000737:chemistry* / Q000378:metabolism; D008049:Lipase / Q000378:metabolism*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D020005:Propanols / Q000737:chemistry* / Q000378:metabolism; D013237:Stereoisomerism
chemical_list: D005656:Fungal Proteins; D007659:Ketones; D007783:Lactones; D020005:Propanols; C006463:allyl alcohol; D003300:Copper; D008049:Lipase; C431349:lipase B, Candida antarctica