Cooperative Rh(II)/Pd(0) Dual-Catalyzed <i>gem-</i>Difunctionalization of α-Diazo Carbonyl Compounds: Construction of Quaternary Carbon Centers

Abstract

The efficient construction of quaternary carbon centers is a challenging task due to their enhanced structural complexity. Although the catalytic gem-difunctionalization of alpha-diazo carbonyl compounds via metal-carbenoids is well-documented, developing new methods to access quaternary carbon centers which are difficult or unattainable in monocatalysis is highly desirable. Dual catalysis where two different catalysts work concurrently has emerged as a powerful strategy to achieve new reactivity and selectivity. In this review, we highlight the recent advances in cooperative Rh(II)/Pd(0) dual catalysis for the construction of quaternary carbon centers, focusing on the synthetic utility of stable alpha-diazo-beta-keto-esters and allylic carboxylates. Additionally, several challenging asymmetric Rh(II)/Pd(0) dual-catalyzed transformations generating chiral quaternary carbon centers are also discussed.