Dual Catalysis in Rhodium(II) Carbenoid Chemistry

Dual catalysis represents an alternative archetype in carbene chemistry that surpasses traditional single catalyst systems. By employing dual catalyst systems, one can improve the efficiency of existing reactions and enable new chemical transformations. Reactions involving dual synergistic catalysis are increasingly valuable as they offer convenient strategies for synthesizing challenging quaternary carbon centers and bioactive core structures. This review article focuses on trapping diazo‐derived, rhodium (II) zwitterionic intermediates with varying electrophiles such as Michael acceptors, alkynes, π‐allyl Pd(II) complexes, and the Nicholas intermediate. This review describes the recent developments of dual catalysis in rhodium (II) carbenoid chemistry, where rhodium is cooperatively working with a second transition metal (Sc/Pd/Ag/Au) or organocatalyst. The redox compatibility, turnover pathways, and the generation of unique rhodium‐bound zwitterionic intermediates make rhodium an attractive partner for dual catalysis reactions to enable new transformations.