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Dinuclear transition-metal catalysis is a distinctive approach for cross-coupling reactions, but Rh(I)–Rh(III) redox catalysis has rarely been considered. Here, a dinuclear Rh(III)–Rh(III) redox ca...

Diazo compounds are popular carbenoid precursors that can react with various transition metals to afford carbene species for further transformations. In this study, density functional theory calcul...

Computational characterization of the oxidation addition promoted in rhodium-catalyzed cyclopropenone activation and conversion via quinolyl-, pyridyl-, and nitrone-directed C–H activation is presented. Our theoretical studies found that a common catalytic cycle for these reactions starts with Rh(III)-mediated concerted metalation–deprotonation or electrophilic deprotonation to afford the aryl-Rh(III) intermediate. Oxidative addition of cyclopropenone to aryl-Rh(III) then gives a cyclorhoda(V)butanone intermediate, leading to the cleavage of the cyclopropene moiety through a concerted three-membered cyclic transition state. Subsequent reductive elimination of the intermediate generates a target C(aryl)–C(acyl) bond. The final product is produced by further transformations with concomitant regeneration of active Rh(III) catalyst. The previously proposed carbonyl insertion mode for the activation of cyclopropenones is excluded by the density functional theory calculations. The directing group effect in cycl...