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N-Heterocyclic Carbene-Catalyzed Oxidations
Brooks E Maki1, Audrey Chan, Eric M Phillips
1Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois, 60208.
Abstract:
N-Heterocyclic carbenes catalyze the oxidation of allylic and benzylic alcohols as well as saturated aldehydes to esters with manganese(IV) oxide in excellent yields. A variety of esters can be synthesized, including protected carboxylates. The oxidation proceeds under mild conditions, with low loadings of a simple triazolium salt pre-catalyst in the presence of base. Substrates containing potentially epimerizable centers are oxidized while preserving stereochemical integrity. The acyl triazolium intermediate generated under catalytic conditions can be employed as a chiral acylating agent in the desymmetrization of meso-diols.
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