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受光照驱动的无需催化剂和氧化还原中性的芳基三氟甲基化和烷基化反应。

Catalyst-Free and Redox-Neutral Innate Trifluoromethylation and Alkylation of Aromatics Enabled by Light.

机构信息

Department of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University , 801 Sherbrooke St. W., Montreal, Quebec H3A 0B8, Canada.

Ministry of Education Key laboratory of Combinatorial Biosynthesis and Drug Discovery, Hubei Provincial Engineering and Technology Research Center for Fluorinated Pharmaceuticals, School of Pharmaceutical Sciences, Wuhan University , Wuhan 430071, China.

出版信息

J Am Chem Soc. 2017 Oct 11;139(40):14315-14321. doi: 10.1021/jacs.7b08685. Epub 2017 Oct 1.

Abstract

The Minisci alkylation is useful to functionalize aromatics via alkyl radical addition. Current approaches to prepare alkyl radicals follow either oxidative or reductive pathways from various functional groups. Developing new strategy beyond these traditional methods remains elusive yet highly significant. In this article, we present a redox-neutral and catalyst-free protocol to engender alkyl radicals in the context of trifluoromethylation and general alkylation of arenes. This protocol, via the Norrish type I concept to produce alkyl radicals, accommodates various functional groups and delivers the product in good yields. This method identified a series of compounds as the trifluoromethylation and alkylation reagents assisted by light. It is expected that these compounds can find potential applications in other radical-involved reactions.

摘要

Minisci 烷基化反应是通过烷基自由基加成来官能化芳烃的有效方法。目前,制备烷基自由基的方法主要是通过各种官能团的氧化或还原途径。开发超越这些传统方法的新策略仍然是一个具有挑战性但非常重要的课题。在本文中,我们提出了一种无氧化还原和无催化剂的方法,在三氟甲基化和芳基的一般烷基化反应中生成烷基自由基。该方法通过 Norrish 型 I 反应生成烷基自由基,适用于各种官能团,并以良好的收率得到产物。该方法确定了一系列化合物作为光辅助的三氟甲基化和烷基化试剂。预计这些化合物可以在其他涉及自由基的反应中找到潜在的应用。

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