Synergistic Strategies of Cyano Migration and Photocatalysis for Difunctionalization of Unactivated Alkenes: Synthesis of Di‐ and Mono‐Fluorinated Alkyl Nitriles

Abstract

A general protocol for the challenging cyanofluoroalkylation of unactivated alkenes is disclosed. A broad range of synthetically useful diand mono-fluorinated alkyl nitriles are readily obtained in good yields under mild reaction conditions. The efficient combination of intramolecular cyano migration and photoredox catalysis significantly expands the field of difunctionalization of olefins.

Alkene 1,2‐Difunctionalization by Radical Alkenyl Migration

“…Vicinal difunctionalization through radical perfluoroalkylation and subsequent intramolecular formyl, aryl, cyano, and heteroaryl migration has been documented previously (Scheme ). Moreover, Zhu and co‐workers and our group reported cascade reactions involving a radical 1,4‐alkynyl‐group migration .…”

Copper‐Catalyzed Heteroarylsilylation of Unactivated Olefins through Distal Heteroaryl Migration

“…There are also a few examples reported with distal aryl migration . Recently, we consecutively studied the migratory aptitude of cyano,– heteroaryl,– imino, formyl, and alkynyl groups, and demonstrated their applications in difunctionalization of unactivated alkenes. For example, we have disclosed the trifluoromethylative heteroarylation of alkenes for the first time (Scheme A) .…”

Selective C-C Bond Scission of Ketones via Visible-Light-Mediated Cerium Catalysis

“…Notably, the radical-mediated migration strategy has recently been elegantly employed in various synthetically valuable transformations by the Zhu group. [58][59][60][61][62][63][64][65][66] Importantly, we posited that the resulting cyanation product would be easily converted to lactams through a simple reductive cyclization. Lactams are biologically significant scaffolds in a variety of complex natural products and pharmaceutical agents.…”