Synthesis 2019; 51(13): 2585-2631
DOI: 10.1055/s-0037-1611784
review
© Georg Thieme Verlag Stuttgart · New York

Rhodium-Catalyzed Allylation Reactions

Mahesh Bhagwan Thoke
a   Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, 350002, P. R. of China   eMail: kangq@fjirsm.ac.cn
b   University of Chinese Academy of Sciences, Beijing, 100049, P. R. of China
,
a   Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, 350002, P. R. of China   eMail: kangq@fjirsm.ac.cn
› Institutsangaben
This work was supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant XDB20000000) and the 100 Talents Program of the Chinese Academy of Sciences. Mahesh B. Thoke delightedly acknowledges the CAS-TWAS President’s Fellowship for Ph.D.
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Publikationsverlauf

Received: 08. März 2019

Accepted after revision: 08. März 2019

Publikationsdatum:
30. April 2019 (online)


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