Photo‐Induced Ruthenium‐Catalyzed Double Remote C(sp²)−H / C(sp³)−H Functionalizations by Radical Relay

Abstract

Abstract Distal C(sp 2 )−H and C(sp 3 )−H functionalizations have recently emerged as step‐economical tools for molecular synthesis. However, while the C(sp 2 )−C(sp 3 ) construction is of fundamental importance, its formation through double remote C(sp 2 )−H/C(sp 3 )−H activation has proven elusive. By merging the ruthenium‐catalyzed meta ‐C(sp 2 )−H functionalization with an aliphatic hydrogen atom transfer (HAT) process, we, herein, describe the catalyzed twofold remote C(sp 2 )−H/C(sp 3 )−H functionalizations via photo‐induced ruthenium‐mediated radical relay. Thus, meta ‐C(sp 2 )−H arene bonds and remote C(sp 3 )−H alkane bonds were activated by a single catalyst in a single operation. This process was accomplished at room temperature by visible light—notably without exogenous photocatalysts. Experimental and computational theory studies uncovered a manifold comprising ortho ‐C−H activation, single‐electron‐transfer (SET), 1, n ‐HAT ( n =5–7) and σ‐activation by means of a single ruthenium(II) catalyst.