Tandem oxidation of allylic and benzylic alcohols to esters catalyzed by N-heterocyclic carbenes.
N-heterocyclic carbenes catalyze the oxidation of allylic, propargylic, and benzylic alcohols to esters with manganese(IV) oxide in excellent yields. A variety of ester derivatives can be synthesized, including protected carboxylates. This one-pot tandem oxidation represents the first organocatalytic oxidation of alcohols to esters. Saturated esters can also be accessed from aldehydes using this method. Through the utilization of a chiral catalyst, the acyl-heteroazolium intermediate becomes a chiral acylating agent, which can desymmetrize meso-1,2-diols. [reaction: see text].
Maki
Brooks E
BE
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA.
Chan
Audrey
A
Phillips
Eric M
EM
Scheidt
Karl A
KA
D000498:Allyl Compounds / Q000737:chemistry*; D001592:Benzyl Alcohols / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006838:Hydrocarbons / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D000498:Allyl Compounds; D001592:Benzyl Alcohols; D004952:Esters; D006571:Heterocyclic Compounds; D006838:Hydrocarbons; C030011:carbene; D008697:Methane