Catalyst‐Directed Selectivity in Vinylcarbene Reactions: A Comparative Study of Ag, Rh, and Cu Complexes

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis Pub Date : 2025-07-13 DOI:10.1002/adsc.70007

Roger Monreal‐Corona, Àlex Díaz‐Jiménez, Pedro J. Pérez, Ana Caballero, Anna Roglans, Albert Poater, Anna Pla‐Quintana

引用次数: 0

Abstract

A comprehensive mechanistic investigation is conducted to uncover the factors governing the selectivity of Ag, Rh, and Cu catalysts in vinylcarbene‐mediated reactions. The study examines the preference for carbenic versus vinylogous C(sp3)H bond insertion, highlighting the critical roles of the electronic and steric properties of transition metal catalysts. Contrary to previous assumptions that the enhanced electrophilic character of the vinylogous position in metal vinyl carbenes is the primary determinant, the findings demonstrate that the stereoelectronic effects of the ligand play a more dominant role. These insights inform the design of catalytic systems with tailored selectivity, advancing predictive catalysis and CH bond functionalization.

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乙烯基乙烯反应的催化剂定向选择性：Ag、Rh和Cu配合物的比较研究

研究了Ag、Rh和Cu催化剂在乙烯基碳烯催化反应中的选择性。该研究考察了碳化合物与葡萄化合物C(sp3) - H键插入的偏好，强调了过渡金属催化剂的电子和空间性质的关键作用。与先前的假设相反，金属乙烯基碳烯中葡萄状位置的亲电性增强是主要决定因素，研究结果表明配体的立体电子效应起着更主要的作用。这些见解为设计具有定制选择性的催化系统提供了信息，促进了预测催化和C - H键功能化。

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

Advanced Synthesis & Catalysis 化学-应用化学

CiteScore

9.40

自引率

7.40%

发文量

447

审稿时长

1.8 months

期刊介绍： Advanced Synthesis & Catalysis (ASC) is the leading primary journal in organic, organometallic, and applied chemistry. The high impact of ASC can be attributed to the unique focus of the journal, which publishes exciting new results from academic and industrial labs on efficient, practical, and environmentally friendly organic synthesis. While homogeneous, heterogeneous, organic, and enzyme catalysis are key technologies to achieve green synthesis, significant contributions to the same goal by synthesis design, reaction techniques, flow chemistry, and continuous processing, multiphase catalysis, green solvents, catalyst immobilization, and recycling, separation science, and process development are also featured in ASC. The Aims and Scope can be found in the Notice to Authors or on the first page of the table of contents in every issue.