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

Distal C(sp² )-H and C(sp³ )-H functionalizations have recently emerged as step-economical tools for molecular synthesis. However, while the C(sp² )-C(sp³ ) construction is of fundamental importance, its formation through double remote C(sp² )-H/C(sp³ )-H activation has proven elusive. By merging the ruthenium-catalyzed meta-C(sp² )-H functionalization with an aliphatic hydrogen atom transfer (HAT) process, we, herein, describe the catalyzed twofold remote C(sp² )-H/C(sp³ )-H functionalizations via photo-induced ruthenium-mediated radical relay. Thus, meta-C(sp² )-H arene bonds and remote C(sp³ )-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.