Benzoyl Peroxide Promoted Radical ortho-Alkylation of Nitrogen Heteroaromatics with Simple Alkanes and Alcohols.

A catalytic amount of benzoyl peroxide initiates a crossdehydrogenative coupling reaction of N-iminopyridine ylides with alkanes and alcohols in a metal-free, open-air system, leading to 2-alkylpyridines with high regioselectivity in moderate to good yields without an additional reduction step to remove the activated group.