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钯催化的 C-N 键活化的去芳构化环羰基化反应。

Palladium-Catalyzed Dearomative Cyclocarbonylation by C-N Bond Activation.

机构信息

State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 (China).

出版信息

Angew Chem Int Ed Engl. 2015 Sep 7;54(37):10912-6. doi: 10.1002/anie.201504805. Epub 2015 Jul 21.

Abstract

A fundamentally novel approach to bioactive quinolizinones is based on the palladium-catalyzed intramolecular cyclocarbonylation of allylamines. [Pd(Xantphos)I2 ], which features a very large bite angle, has been found to facilitate the rapid carbonylation of azaarene-substituted allylamines into bioactive quinolizinones in good to excellent yields. This transformation represents the first dearomative carbonylation and is proposed to proceed by palladium-catalyzed CN bond activation, dearomatization, CO insertion, and a Heck reaction.

摘要

一种基于钯催化的烯丙胺分子内环羰化反应来合成具有生物活性的喹啉酮的全新方法。研究发现,具有非常大的 bite angle 的[Pd(Xantphos)I2]可以促进氮杂芳烃取代的烯丙胺快速转化为具有生物活性的喹啉酮,产率良好到优秀。这种转化代表了首例去芳构化的羰基化反应,其反应历程被认为是钯催化的 CN 键活化、去芳构化、CO 插入和 Heck 反应。

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