Rhenium(I)‐Catalyzed ortho ‐C−H Addition to Bicyclic Alkenes

Hydroarylation of bicyclic alkenes has been developed using a low-valent ReI -catalyzed, directing group-assisted C-H bond activation strategy. The addition of sodium acetate significantly improves the reaction efficiency; moreover, bicyclic alkenes such as 7-oxa and aza benzonorbornadienes worked efficiently under this reaction condition. Preliminary mechanistic studies suggest that, after the alkene insertion, the rhenacycle preferentially undergoes protonolysis rather than reductive elimination.