Annulation Producing Diverse Heterocycles Promoted by Cobalt Hydride

IF 13.1 1区 化学 Q1 CHEMISTRY, PHYSICAL
Takuma Sugimura, Ren Yamada, Wataru Kanna, Tsuyoshi Mita, Satoshi Maeda, Bartłomiej Szarłan and Hiroki Shigehisa*, 
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引用次数: 0

Abstract

This study demonstrates the efficient synthesis of various heterocycles using the metal hydrogen atom transfer (MHAT)/radical-polar crossover (RPC) method, emphasizing its versatility under mild conditions with high functional group tolerance. By distinguishing between cyclization and annulation, we underscore the complexity and efficiency of this approach in constructing intricate molecular architectures. Notably, the incorporation of an acetone solvent in the formation of cyclic acetal dioxanes from homoallylic alcohols reveals a unique annulation mechanism. Extensive substrate scope analysis and density functional theory calculations provide insights into reaction pathways, highlighting the critical role of cationic alkylcobalt(IV) intermediates and collidine in product selectivity. This study elucidates the mechanisms of the MHAT/RPC method and showcases its potential as a robust alternative to conventional synthetic strategies.

Abstract Image

在氢化钴的促进下嵌合生成多种杂环
本研究展示了利用金属氢原子转移(MHAT)/自由基-极性交叉(RPC)方法高效合成各种杂环的过程,强调了该方法在温和条件下的多功能性和对官能团的高耐受性。通过区分环化和环化,我们强调了这种方法在构建复杂分子结构方面的复杂性和高效性。值得注意的是,在从均烯丙基醇形成环缩醛二恶烷的过程中加入丙酮溶剂,揭示了一种独特的环化机制。广泛的底物范围分析和密度泛函理论计算深入揭示了反应途径,凸显了阳离子烷基钴(IV)中间体和联苯胺在产物选择性中的关键作用。这项研究阐明了 MHAT/RPC 方法的机理,并展示了其作为传统合成策略的可靠替代方法的潜力。
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来源期刊
ACS Catalysis
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.
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