Although methylation reactions are commonplace, current methods require hazardous, toxic, and/or unstable reagents. Two strategies to replace existing methylating agents in reactions with oxygen and carbon nucleophiles will be described. In the first, dimethyl carbonate is used as a non-toxic and "green" electrophilic reagent for the methylation of carboxylic acids. Mechanistic studies suggest that the reaction proceeds by direct methyl transfer from dimethyl carbonate to the nucleophile, in analogy to other electrophilic alkylating agents. In the second strategy, a nucleophilic methylating reagent is used in place of typical electrophilic methyl sources. Cu complexes mediate the oxidative coupling of methylboronic acid with carboxylic acids, phenols, and electron-rich arenes in “Chan-Lam”-type processes.

Methyl transfer from methylboronic acid or dimethyl carbonate for O-H and C-H alkylation

254th National Meeting (2017)

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