Axial‐to‐central chirality transfer is an important strategy to construct chiral centers, where the axially chiral reagents are mostly limited to atropomerically stable ones. Reported herein is a RhIII‐catalyzed enantioselective spiroannulative synthesis of nitrones. The coupling proceeds via C−H arylation to give an atropomerically metastable biaryl, followed by intramolecular dearomative trapping under oxidative conditions with high degree of chirality transfer.

Rhodium(III)-catalyzed C−H activation-based arylation of sterically hindered (hetero)arenes has been realized using diazo compounds and triazoles as arylating reagents for atroposelective synthesis of two classes of biaryls. The coupling of 3substituted indoles and N-sulfonyltriazoles afforded indoles with a C(2)−C chiral axis, while the arylation of 1-naphthylthioether with ortho-quinone diazide afforded chiral binaphthyls. These coupling systems proceeded under mild conditions via C−H activation and carbene insertion despite the steric hindrance of both the arenes and the carbene precursors.

Axial-to-central chirality transfer is an important strategy to construct chiral centers, where the axially chiral reagents are mostly limited to atropomerically stable ones. Reported herein is a Rh III -catalyzed enantioselective spiroannulative synthesis of nitrones. The coupling proceeds via CÀH arylation to give an atropomerically metastable biaryl, followed by intramolecular dearomative trapping under oxidative conditions with high degree of chirality transfer. Scheme 1. CÀH activation and chirality transfer.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Rhodium-catalyzed enantioselective C-H alkynylation of achiral and racemic sulfoxides is disclosed with alkynyl bromide as the alkynylating reagent. A wide range of chiral sulfoxides have been constructed in good yield...