Rhodium-Catalyzed Atroposelective Oxidative C–H/C–H Cross-Coupling Reaction of 1‑Aryl Isoquinoline Derivatives with Electron-Rich Heteroarenes

Rhodium­(III)-catalyzed
enantio­selective oxidative C–H/C–H
cross-coupling reaction between two arenes is disclosed. With the
combination of a chiral CpRh­(III) complex and a chiral carboxylic
acid additive, the direct coupling reactions between 1-aryl isoquinoline
derivatives and electron-rich hetero­arenes such as thiophenes,
furans, benzo­thiophenes, and benzo­furans are realized
via a double C–H functionalization process. A series of axially
chiral compounds are obtained in excellent yields and enantio­selectivities
(up to 99% yield and 99% ee). Mechanistic studies suggest that both
C–H bond cleavages may not be the turnover-limiting step.