A free-radical design featuring an intramolecular migration for a synthetically versatile alkyl–(hetero)arylation of simple olefins
Dylan J. Babcock, Andrew J. Wolfram, Jaxon L. Barney, Santino M. Servagno, Ayush Sharma, Eric D. Nacsa
Abstract
, without requiring directing or electronically activating groups) for the first time. Key advances also included the introduction of synthetically diversifiable alkyl groups featuring different degrees of substitution, good diastereocontrol in both cyclic and acyclic settings, the addition of biologically valuable heteroarenes featuring Lewis basic nitrogen atoms as well as simple benzenes, and the generation of either tertiary or quaternary benzylic centers. The synthetic potential of this transformation was demonstrated by leveraging it as the key step in a concise synthesis of oliceridine, a new painkiller that received FDA approval in 2020.