Cooperative Rh(II)/Pd(0) Dual‐Catalyzed gem‐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 α ‐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 α ‐diazo‐ β ‐keto‐esters and allylic carboxylates. Additionally, several challenging asymmetric Rh(II)/Pd(0) dual‐catalyzed transformations generating chiral quaternary carbon centers are also discussed.