Divergent Geminal Alkynylation–Allylation and Acylation–Allylation of Carbenes: Evolution and Roles of Two Transition-Metal Catalysts,Journal of the American Chemical Society

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Divergent Geminal Alkynylation–Allylation and Acylation–Allylation of Carbenes: Evolution and Roles of Two Transition-Metal Catalysts
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-02-08 , DOI: 10.1021/jacs.3c12162
Hongda Chen ₁ , Wenhan Yang ₁ , Jinyu Zhang ₁ , Bin Lu ₁ , Xiaoming Wang _{1,

2}

Affiliation

Cooperative bimetallic catalysis to access novel reactivities is a powerful strategy for reaction development in transition-metal-catalyzed chemistry. Particularly, elucidation of the evolution of two transition-metal catalysts and understanding their roles in dual catalysis are among the most fundamental goals for bimetallic catalysis. Herein, a novel three-component reaction of a terminal alkyne, a diazo ester, and an allylic carbonate was successfully developed via cooperative Cu/Rh catalysis with Xantphos as the ligand, providing a highly efficient strategy to access 1,5-enynes with an all-carbon quaternary center that can be used as immediate synthetic precursors for complex cyclic molecules. Notably, a Meyer–Schuster rearrangement was involved in the reactions using propargylic alcohols, resulting in an unprecedented acylation–allylation of carbenes. Mechanistic studies suggested that in the course of the reaction Cu(I) species might aggregate to some types of Cu clusters and nanoparticles (NPs), while the Rh(II)₂ precursor can dissociate to mono-Rh species, wherein Cu NPs are proposed to be responsible for the alkynylation of carbenes and work in cooperation with Xantphos-coordinated dirhodium(II) or Rh(I)-catalyzed allylic alkylation.

中文翻译：

卡宾的不同双炔基化-烯丙基化和酰化-烯丙基化：两种过渡金属催化剂的演变和作用

协同双金属催化获得新的反应性是过渡金属催化化学反应发展的有力策略。特别是，阐明两种过渡金属催化剂的演变并了解它们在双催化中的作用是双金属催化最基本的目标之一。在此，以 Xantphos 为配体，通过 Cu/Rh 协同催化，成功开发了末端炔烃、重氮酯和烯丙基碳酸酯的新型三组分反应，为以 Xantphos 为配体获得 1,5-烯炔提供了一种高效的策略。全碳四元中心，可用作复杂环状分子的直接合成前体。值得注意的是，使用炔丙醇的反应涉及迈耶-舒斯特重排，导致卡宾前所未有的酰化-烯丙基化。机理研究表明，在反应过程中，Cu(I) 物质可能聚集成某些类型的 Cu 簇和纳米颗粒 (NP)，而 Rh(II) ₂前体可以解离为单 Rh 物质，其中提出了 Cu NP负责卡宾的炔基化，并与 Xantphos 配位的二铑(II) 或 Rh(I) 催化的烯丙基烷基化合作。

更新日期：2024-02-08

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