Catalytic Strategy for Regioselective Arylethylamine Synthesis.

A mild, modular, and practical catalytic system for the synthesis of the highly privileged phenethylamine pharmacophore is reported. Using a unique combination of organic catalysts to promote the transfer of electrons and hydrogen atoms, this system performs direct hydroarylation of vinyl amine derivatives with a wide range of aryl halides (including aryl chlorides). This general and highly chemoselective protocol delivers a broad range of arylethylamine products with complete regiocontrol.

Radical Hydroarylation of Functionalized Olefins and Mechanistic Investigation of Photocatalytic Pyridyl Radical Reactions.

We report the photoredox alkylation of halopyridines using functionalized alkene and alkyne building blocks. Selective single-electron reduction of the halogenated pyridines provides the corresponding heteroaryl radicals, which undergo anti-Markovnikov addition to the alkene substrates. The system is shown to be mild and tolerant of a variety of alkene and alkyne subtypes.

Anti-Markovnikov Hydroarylation of Unactivated Olefins via Pyridyl Radical Intermediates.

The intermolecular alkylation of pyridine units with simple alkenes has been achieved via a photoredox radical mechanism. This process occurs with complete regiocontrol, where single-electron reduction of halogenated pyridines regiospecifically yields the corresponding radicals in a programmed fashion, and radical addition to alkene substrates occurs with exclusive anti-Markovnikov selectivity. This system is mild, tolerant of many functional groups, and effective for the preparation of a wide range of complex alkylpyridines.