中科院上海有机化学研究所王晓明团队探明了dihodium (II)/ xantphos催化的碳烯插入和烯丙基烷基化过程。相关研究成果发表在2021年7月23日出版的国际知名学术期刊《美国化学会杂志》。

尽管在有机合成中，dihodium催化的重氮化合物、亲核试剂和亲电试剂的多组分反应取得了很大进展，但通过烯丙基金属中间体引入烯丙基作为第三组分仍然是该领域的一个巨大挑战。

该文中，研究人员揭示了一种通过新的dirhodium(II)/Xantphos催化实现的易于获得的胺、重氮化合物和烯丙基化合物的有吸引力的三组分反应，以高原子和更加经济的良好产率提供各种结构复杂和功能多样的α-四元α-氨基酸衍生物。机理研究表明，该转化是通过接力dirhodium(II)催化卡宾插入和烯丙基烷基化反应实现的，dihodium与Xantphos的配位作用有效地改善了dirhodium的催化性能，使催化烯丙基烷基化反应具有良好的活性。

附：英文原文

Title: Dirhodium(II)/Xantphos-Catalyzed Relay Carbene Insertion and Allylic Alkylation Process: Reaction Development and Mechanistic Insights

Author: Bin Lu, Xinyi Liang, Jinyu Zhang, Zijian Wang, Qian Peng, Xiaoming Wang

Issue&Volume: July 23, 2021

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.

DOI: 10.1021/jacs.1c05701

Source: https://pubs.acs.org/doi/10.1021/jacs.1c05701