Correction: Catalytic generation of -quinone dimethides donor/donor rhodium carbenes.

[This corrects the article DOI: 10.1039/D3SC00734K.].

Catalytic generation of -quinone dimethides donor/donor rhodium carbenes.

Substrates engineered to undergo a 1,4-C-H insertion to yield benzocyclobutenes resulted in a novel elimination reaction to yield -quinone dimethide (-QDM) intermediates that undergo Diels-Alder or hetero-Diels-Alder cycloadditions. The analogous benzylic acetals or ethers avoid the C-H insertion pathway completely and, after hydride transfer, undergo a de-aromatizing elimination reaction to -QDM at ambient temperature. The resulting dienes undergo a variety of cycloaddition reactions with high diastereo- and regio-selectivity.

Divergent stereochemical outcomes in the insertion of donor/donor carbenes into the C-H bonds of stereogenic centers.

Intramolecular C-H insertions with donor/donor dirhodium carbenes provide a concise and highly stereoselective method to set two contiguous stereocenters in a single step. Herein, we report the insertion of donor/donor carbenes into stereogenic carbon centers allowing access to trisubstituted benzodihydrofurans in a single step. This study illuminates, for the first time, the stereochemical impact on the carbene center and delineates the structural factors that enable control over both stereogenic centers.