对映选择性、需氧铜催化的未活化烯烃的分子内碳胺化和碳醚化反应
Enantioselective, Aerobic Copper-Catalyzed Intramolecular Carboamination and Carboetherification of Unactivated Alkenes.
作者信息
Wdowik Tomasz, Galster Samuel L, Carmo Raul L L, Chemler Sherry R
机构信息
Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260, United States.
出版信息
ACS Catal. 2020 Aug 7;10(15):8535-8541. doi: 10.1021/acscatal.0c02607. Epub 2020 Jul 16.
Abstract
Reduction of waste is an important goal of modern organic synthesis. We report herein oxidase reactivity for enantioselective intramolecular copper-catalyzed alkene carboamination and carboetherification reactions where previously used stoichiometric MnO has been replaced with oxygen. This substitution was risky as the reaction mechanism is thought to involve C-C bond formation via addition of alkyl carbon radicals to arenes. Such intermediates are also susceptible to C-O bond formation via O addition. Control of absolute stereochemistry under aerobic conditions was also uncertain. The oxidative cyclization efficiencies appear to track with the ease of the radical addition to the arenes.
摘要
减少废弃物是现代有机合成的一个重要目标。我们在此报告了氧化酶在对映选择性分子内铜催化的烯烃碳胺化和碳醚化反应中的反应活性，其中先前使用的化学计量的MnO已被氧气取代。这种替代是有风险的，因为反应机理被认为涉及通过将烷基碳自由基加成到芳烃上形成C-C键。这类中间体也容易通过氧加成形成C-O键。在有氧条件下对绝对立体化学的控制也不确定。氧化环化效率似乎与自由基加成到芳烃的难易程度相关。
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