A Rh­(II)/Pd(0) dual-catalysis strategy that promotes the regio-divergent transformations of alkylic oxonium ylides from α-diazo-β-ketoesters has been developed. Polyfunctionalized dihydrofuran-3-ones with an O-substituted quaternary carbon center and 2,3-disubstituted benzofurans can be selectively obtained in good to excellent yields at room temperature via one-pot synthesis. The reaction mechanism was further investigated by the control, stepwise, and crossover experiments.

A chemo-selective Rh(II)/Pd(0) dual catalysis that promotes one-pot synthesis of C3quaternary allylic oxindoles from N-aryl-a-diazo-bketoamides and functionalized allyl carbonates in good to excellent yields has been developed. The efficiency of this transformation relies on the choice of Rh(II)/Pd(0) dual catalysis strategy that enabled cascade intramolecular aryl CÀH insertion and allylic alkylation under mild conditions.