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从铜介导的芳基-炔烃和芳基碘代-炔烃交叉偶联反应构建 C(芳基)-C(炔基)键:芳基 C-H 活化和 Castro-Stephens 反应中的共同芳基-Cu(III)中间体。

Construction of C(aryl)-C(alkynyl) bond from copper-mediated arene-alkyne and aryl iodide-alkyne cross-coupling reactions: a common aryl-Cu(III) intermediate in arene C-H activation and Castro-Stephens reaction.

机构信息

MOE Key Laboratory of Bioorganic Phosphorous Chemistry and Chemical Biology, Department of Chemistry, Tsinghua University, Beijing 100084, China.

出版信息

Org Lett. 2012 Mar 16;14(6):1472-5. doi: 10.1021/ol300205r. Epub 2012 Mar 5.

DOI:10.1021/ol300205r
PMID:22390769
Abstract

Both copper(II)-mediated oxidative C-H bond activation and oxidative addition of copper(I) into a C-I bond produced an identical and structurally well-defined aryl-Cu(III) intermediate. The cross-coupling reaction of an aryl-Cu(III) intermediate with both terminal alkynes at an elevated temperature and alkynyllithium reagents under mild conditions led effectively to the formation of a C(aryl)-C(alkynyl) bond. An alternative mechanism has been proposed for the Castro-Stephens reaction.

摘要

铜(II)介导的氧化 C-H 键活化和氧化加成铜(I)进入 C-I 键产生了相同的、结构定义良好的芳基-Cu(III)中间体。芳基-Cu(III)中间体与末端炔烃在高温下以及在温和条件下与炔基锂试剂的交叉偶联反应有效地导致了 C(芳基)-C(炔基)键的形成。已经为 Castro-Stephens 反应提出了一种替代机制。

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