The Journal of Organic Chemistry
Although methylation reactions are commonplace, currently used reagents are hazardous, toxic, and/or unstable. Dimethylcarbonate has been put forth as an inexpensive, nontoxic, and “green” potential methylating reagent. Herein we report a general, base-catalyzed methyl transfer from dimethylcarbonate to carboxylic acids. High selectivity for esterification is observed even in the presence of unprotected phenols, and the mild reaction conditions enable conservation of stereochemistry at epimerizable stereocenters. Isotope-labeling studies suggest a mechanism proceeding by direct methyl transfer from dimethylcarbonate to the substrate.
“This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jo401941v
Ji, Yuan; Sweeney, Jessica; Zoglio, Jillian; and Gorin, David J., "Catalytic Methyl Transfer from Dimethylcarbonate to Carboxylic Acids" (2013). Chemistry: Faculty Publications, Smith College, Northampton, MA.
Peer reviewed accepted manuscript.