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Mechanism of Z-Selective Hydroalkylation of Terminal Alkynes

Journal of the American Chemical Society(2021)SCI 1区

Univ Washington

Cited 9|Views6
Abstract
This paper describes a detailed mechanistic study of the silver-catalyzed Z-selective hydroalkylation of terminal alkynes. Considering the established mechanistic paradigms for Z-selective hydroalkylation of alkynes, we explored a mechanism based on the radical carbometalation of alkynes. Experimental results have provided strong evidence against the initially proposed radical mechanism and have led us to propose a new mechanism for the Z-selective hydroalkylation of alkynes based on boronate formation and a 1,2-metalate shift. The new mechanism provides a rationale for the excellent Z-selectivity observed in the reaction. A series of stoichiometric experiments has probed the feasibility of the proposed elementary steps and revealed an additional role of the silver catalyst in the protodeboration of an intermediate. Finally, a series of kinetic measurements, KIE experiments, and competition experiments allowed us to identify the turnover limiting step and the resting state of the catalyst. We believe that the results of this study will be useful in the further exploration and development of related transformations of alkynes.
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alkynes,mechanism
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要点】:本文详细研究了银催化的末端炔烃Z选择性氢烷基化反应机制,提出了基于硼酸酯形成和1,2-金属迁移的新机制,为反应的高Z选择性提供了理论依据。

方法】:通过一系列的定量实验探索了所提出反应步骤的可行性,并结合动力学测量、同位素效应实验和竞争实验揭示了反应的限制步骤和催化剂的静止状态。

实验】:实验使用了末端炔烃为底物,在银催化下进行反应,通过一系列的实验证据排除了起初提出的自由基机制,确证了新的反应机制,并测定了相关的催化参数。