Rhodium-Catalyzed Allylation Reactions

Abstract Rhodium-catalyzed allylation reactions are well known for their unique selectivity and reactivity due to the high memory effect of Rh as compared to other metals. These reactions involve the substitution of allylic rhodium intermediates with a diverse range of different nucleophiles, leading to C–C and C–heteroatom bond formation. Modern organic chemists are, however, interested in atom-economical protocols under greener pathways and following recent increased understanding of mechanistic aspects of Rh-catalyzed allylation via the hydrofunctionalization of allenes or alkynes, great strides have made in the design and development of new atom-economical protocols. In this article, we review this field from its beginning to current state. 1 Introduction 2 Rhodium-Catalyzed Allylic Substitution 3 Rhodium-Catalyzed Allylation with Allenes 4 Rhodium-Catalyzed Allylation with Alkynes 5 Rhodium-Catalyzed Allylation with Dienes 6 Rhodium-Catalyzed Allylation by ARO of Oxabicyclic Alkenes 7 Rhodium-Catalyzed Enantioselective Allylation in Natural Product and Drug Synthesis 8 Conclusion