Experimental and Computational Studies on Cp*CyRh(III)/KOPiv-Catalyzed Intramolecular Dehydrogenative Cross-Couplings for Building Eight-Membered Sultam/Lactam Frameworks.,Organic Letters

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Experimental and Computational Studies on Cp*CyRh(III)/KOPiv-Catalyzed Intramolecular Dehydrogenative Cross-Couplings for Building Eight-Membered Sultam/Lactam Frameworks.
Organic Letters ( IF 4.9 ) Pub Date : 2020-07-01 , DOI: 10.1021/acs.orglett.0c01823
Liping Li ₁ , Hui Gao ₁ , Ming Sun ₁ , Zhi Zhou ₁ , Wei Yi ₁

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Described herein is an unusual Cp^*CyRh(III)-catalyzed intramolecular site-specific aryl C–H annulation, a highly chemoselective protocol providing direct access to eight-membered sultams/lactams with broad substrate/functional group tolerance. Experimental and computational studies reveal that such a transformation involves a unique PivOH-assisted aryl C–H activation/alkene insertion/β-H elimination/hydrogen-transfer process involving the Rh(III)–hydride species as the active intermediate with the concomitant release of H₂ as the major byproduct, thus enabling the developed Cp^*CyRh(III) catalysis with redox-neutral and highly atom-economical features.

中文翻译：

Cp * CyRh（III）/ KOPiv催化的分子内脱氢交叉偶联用于构建八元Sultam / Lactam骨架的实验和计算研究。

本文描述的是一种不寻常的Cp ^{* Cy} Rh（III）催化的分子内位点特异性芳基C–H环化反应，一种高度化学选择性的实验方案，可直接获得具有广泛的底物/官能团耐受性的八元sultams / lactams。实验和计算研究表明，这种转化涉及独特的PivOH辅助的芳基CH活化/烯烃插入/β-H消除/氢转移过程，其中Rh（III）-氢化物为活性中间体，并伴随释放H ₂作为主要副产物，因此可以实现具有氧化还原中性和高度原子经济特性的发达的Cp ^{* Cy} Rh（III）催化。

更新日期：2020-07-17

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