硝酮的催化迁移氧化偶联。

Catalytic migratory oxidative coupling of nitrones.

机构信息

Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1, Hongo, Tokyo 113-0033, Japan.

出版信息

Org Lett. 2011 Aug 19;13(16):4288-91. doi: 10.1021/ol201629n. Epub 2011 Jul 18.

DOI:10.1021/ol201629n

Abstract

A Cu(I)-catalyzed migratory oxidative coupling between nitrones and heterocycles or a methylamine is described. Selective C-C bond-formation proceeds through cleavage of two C(sp(3))-H bonds concomitant with C═N double bond-migration. The reaction provides an alternating nitrone moiety, allowing for further synthetically useful transformations. Radical clock studies suggest that the nucleophilic addition of nitrones to an oxidatively generated carbocation is a key step.

摘要

本文描述了一种 Cu(I)催化的氮氧自由基与杂环或甲胺之间的迁移氧化偶联反应。通过同时断裂两个 C(sp(3))-H 键和 C═N 双键迁移，实现了选择性的 C-C 键形成。该反应提供了交替的氮氧自由基部分，允许进一步进行具有合成用途的转化。自由基钟研究表明，氮氧自由基对氧化生成的碳正离子的亲核加成是关键步骤。