Site‐Selective C(sp³)−H Borylation of 3‐Azabicyclo[3.1.0]hexanes by Cooperative Iridium/Aluminum Catalysis

Abstract

Functionalized 3‐azabicyclo[3.1.0]hexanes are highly interesting for their physiochemical and pharmacological properties. We report an unprecedented direct bridge‐head C(sp3)−H borylation by cooperative iridium/aluminum catalysis. This reaction proceeds under mild conditions in good yields with moderate to complete site selectivities. Moreover, the use of a BINOL‐based chiral aluminum catalyst renders the synthesis of enantioenriched alkylboronate products. We also disclose its synthetic utility through rapid diversifications without any loss of the stereochemical information.