Synergetic Cp*Rh(III)/Zn2+-Prompted Arylamination of Alkylalkenes: Reaction Development and Mechanistic Insight

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-07-23 DOI:10.1021/acscatal.5c03096

Zhi Zhou, Zhihuan Peng, Weijie Chen, Xuebing Chen, Huiying Xu, LeongChing Wong, Zhongyi Zeng, Hui Gao, Wei Yi

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引用次数: 0

Abstract

Arylethylamines are not only privileged intermediates in organic synthesis but also a type of core structural motif widely found in both pharmaceutical and material sciences. Therefore, there is an urgent need to develop practical and straightforward strategies toward their synthesis, among which the carboamination of ubiquitous alkenes should be one of the most ideal strategies, but it still represents great challenges, especially for alkylalkenes, due to their relatively inert reactivity and elusive chemoselectivity control. We report herein a mild, redox-neutral, and chemo-/regioselective Cp*Rh(III)-catalyzed arylamination of diverse unactivated alkylalkenes by judicious choice of N-phenoxy amides as both the C- and N-sources and ZnCl₂ as the master additive, whereby two classical and alternative β-H elimination pathways are completely suppressed; instead, the carboamination scenario is delivered in a controllable and highly selective manner. Through a combined computational and experimental mechanistic study, the unique synergetic catalytic mode mediated by the additive effect is reasonably clarified, thereby providing a solid reference for modern synergistic catalytic C–H functionalization chemistry.

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协同Cp*Rh(III)/Zn2+促进的烷基烯芳基层化：反应发展和机理的见解

芳基乙胺不仅是有机合成的重要中间体，也是广泛应用于制药和材料科学的一类核心结构基序。因此，迫切需要开发实用而直接的合成策略，其中普遍存在的烯烃的碳胺化应该是最理想的策略之一，但由于其相对惰性的反应活性和难以捉摸的化学选择性控制，它仍然代表着巨大的挑战，特别是对于烷基烯烃。本文报道了一种温和的、氧化还原中性的、化学/区域选择性的Cp*Rh（III）催化的多种未活化烷基烯的芳基化反应，通过明智地选择n -苯氧基酰胺作为C源和n源，并选择ZnCl2作为主添加剂，从而完全抑制了两种经典和替代的β-H消除途径；相反，碳胺化过程是以一种可控和高度选择性的方式进行的。通过计算与实验相结合的机理研究，合理阐明了加性效应介导的独特协同催化模式，从而为现代协同催化C-H功能化化学提供了坚实的参考。

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

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.