Rhodium-Catalyzed [5 + 1 + 2] Reaction of Yne-Vinylcyclopropenes and CO: The Application of Vinylcyclopropenes for Higher-Order Cycloaddition

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-04-30 DOI:10.1021/jacs.5c02041

Zhiqiang Huang, Zhi-Xiang Yu

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Abstract

Transition metal-catalyzed higher-order cycloadditions involving vinylcyclopropenes (VCPEs) have not been realized to synthesize challenging medium-sized rings, partially due to their poor stability and many competing side reactions. We report here a Rh-catalyzed [5 + 1 + 2] reaction of yne-VCPEs and CO for the synthesis of eight-membered carbocycles with trienone moiety, which so far can be accessed by only limited reactions. The key to this higher-order cycloaddition is that once C–C cleavage of VCPE (C₅ synthon) to form a six-membered metallacycle is initiated, CO (C₁ synthon) insertion happens before alkyne (C₂ synthon) insertion, attributing to the special reactivity of the sp² carbon in the vinylcyclopropene. Quantum chemical calculations have been applied to support this reaction pathway. The present [5 + 1 + 2] reaction has a broad scope, and the C₂ synthon can also be extended to alkenes and allene. Of the same importance, the present reaction can be catalyzed by either [Rh(CO)₂Cl]₂ or a cheaper complex, RhCl₃·nH₂O.

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铑催化乙烯基环丙烯与CO的[5 + 1 + 2]反应：乙烯基环丙烯在高阶环加成中的应用

过渡金属催化的含乙烯基环丙烯（vcpe）的高阶环加成尚未实现，以合成具有挑战性的中型环，部分原因是它们的稳定性差和许多竞争性副反应。本文报道了rh催化的炔- vcpes和CO的[5 + 1 + 2]反应，用于合成具有三烯酮部分的八元碳环，迄今为止只能通过有限的反应获得。这种高阶环加成的关键在于，一旦VCPE （C5合子）的C-C裂解形成六元金属环，由于乙烯基环丙烯中sp2碳的特殊反应活性，CO （C1合子）的插入发生在炔（C2合子）插入之前。量子化学计算已被应用于支持这一反应途径。目前的[5 + 1 + 2]反应范围广，C2合子也可以扩展到烯烃和烯。同样重要的是，目前的反应可以由[Rh(CO)2Cl]2或更便宜的配合物RhCl3·nH2O催化。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.