The Ullmann reaction to form C–N bonds, first described over a century ago, is now a classic method in organic synthesis. During the time since its discovery, there had been no reports of a photoinduced variant. Instead, copper-mediated and copper-catalyzed processes have generally been effected with the aid of heat (e.g., at 60–120 °C). Recently, we have established that a photoinduced Ullmann C–N arylation can proceed at a temperature as low as –40 °C. The reaction of an amine with an alkyl halide is a classic “textbook” approach to C–N bond construction. For efficient C–N bond formation, the electrophile should generally be a good substrate for an SN2 reaction. A mild, transition metal-catalyzed N-alkylation that proceeds through a radical pathway for C–X cleavage has the potential to address important limitations of the classic SN2 approach. In this lecture, recent efforts to address this challenge will be described.

Photoinduced, copper-catalyzed coupling reaction

249th National Meeting (2015)

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