Relay Rh(II)/Pd(0) Dual Catalysis: Selective Construction of Cyclic All-Quaternary Carbon Centers

A novel relay Rh­(II)/Pd(0) dual catalysis strategy that promotes the divergent reaction of α-diazo-carbonyl compounds with allylic carboxylates for the selective construction of cyclic all-quaternary carbon centers has been developed. This binary catalyst system rendered domino C–H insertion/allylic alkylation process under mild conditions. Remarkably, the domino catalytic reaction shows good selectivity and excellent tolerance to various functionalities and is operationally simple.