Base-Mediated Alkylation of Pyrimidines via Sulfur Deletion.

We report the alkylation of N-heterocycles by the sulfur deletion of aryl-alkyl sulfones. Strategic C(sp2)-C(sp3) bond formation is achieved via the base-mediated extrusion of sulfur dioxide to give N-heterocyclic benzylic anions. This structural-editing methodology employs mild reaction conditions and is compatible with various functional groups, including aryl halides, which can be utilized for further synthetic transformations. We demonstrate that the transient benzylic anions formed in this transformation can be trapped with various electrophiles in a library-amenable protocol, allowing for the expedient structural diversification of biologically relevant heterocycles.