Dirhodium(II)/Xantphos-Catalyzed Relay Carbene Insertion and Allylic Alkylation Process: Reaction Development and Mechanistic Insights
- 23 July 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 143 (30), 11799-11810
- https://doi.org/10.1021/jacs.1c05701
Abstract
Although dirhodium-catalyzed multicomponent reactions of diazo compounds, nucleophiles and electrophiles have achieved great advance in organic synthesis, the introduction of allylic moiety as the third component via allylic metal intermediate remains a formidable challenge in this area. Herein, an attractive three-component reaction of readily accessible amines, diazo compounds, and allylic compounds enabled by a novel dirhodium(II)/Xantphos catalysis is disclosed, affording various architecturally complex and functionally diverse α-quaternary α-amino acid derivatives in good yields with high atom and step economy. Mechanistic studies indicate that the transformation is achieved through a relay dirhodium(II)-catalyzed carbene insertion and allylic alkylation process, in which the catalytic properties of dirhodium are effectively modified by the coordination with Xantphos, leading to good activity in the catalytic allylic alkylation process.Funding Information
- Natural Science Foundation of Tianjin City (18JCYBJC21400, 19JCJQJC62300)
- National Natural Science Foundation of China (21821002, 21890722, 21950410519)
- Tianjin Research Innovation Project for Postgraduate Students (2019YJSB081)
- Frontiers Science Center for New Organic Matter of Nankai University (63181206)
- Shanghai Pujiang Program (19PJ1411500)
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