Remote C(sp 3 )−H Arylation and Vinylation of N ‐Alkoxypyridinium Salts to δ‐Aryl and δ‐Vinyl Alcohols

The reaction of readily available and benchstable N-alkoxypyridinium salts with arylboronic and vinylboronic acids afforded d-aryl and d-vinyl alcohols, respectively, in the presence of fac-Ir(ppy)3 and Cu(OTf)2 dual catalysts. The reaction takes place through a domino process involving the reductive generation of alkoxyl radicals, 1,5-hydrogen atom transfer (1,5-HAT) and the copper-catalyzed cross-coupling reaction of the resulting translocated carbon radicals with boronic acids. Complementary to the Minisci reaction, this method allows for the arylation of nucleophilic alkyl radicals with both electron-rich and electron-poor arenes under mild reaction conditions.