钯催化氮的c2选择性C−H胺化研究

Qikun Wu, Prof. Dr. Kei Muto, Prof. Dr. Junichiro Yamaguchi
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引用次数: 0

摘要

由于氨基嘧啶在生物重要化合物中的广泛应用,嘧啶的位点选择性C - H胺化是一个关键的挑战。在这项工作中,我们报告了一种概念上新颖的方法,使用邻苯甲酰羟胺,在苯钯络合物的催化下,对嘧啶进行亲电性的c2选择性C - H胺化。这一转变的一个关键特征是通过一个苯基-钯中间体形成远端C - N键,在嘧啶上的丙二酸取代基作为远程导向基团促进了这一转变。这种策略有效地克服了在亲电性的C2-C−H胺化中观察到的固有极性不匹配。该反应具有较高的位点选择性和对胺敏感官能团的选择性,具有较高的合成实用性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

An Umpolung Approach for C2-Selective C−H Amination of Azines by Palladium Catalysis

An Umpolung Approach for C2-Selective C−H Amination of Azines by Palladium Catalysis

The site-selective C−H amination of azines is a critical challenge due to the broad applications of amino azines in biologically important compounds. In this work, we report a conceptually novel approach to the electrophilic C2-selective C−H amination of azines using O-benzoylhydroxylamines, catalyzed by a benzyl–palladium complex. A key feature of this transformation is the formation of the distal C−N bond via a benzyl–Pd intermediate, facilitated by a malonate substituent on the azine as a remote directing group. This strategy effectively overrides the inherent polarity mismatch typically observed in electrophilic C2-C−H aminations. The reaction exhibits high site-selectivity and demonstrates towards amine-sensitive functional group, highlighting its synthetic utility.

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