A General Catalyst for Site-Selective C(sp3)–H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp3)–H Bonds

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• 作者：Ryan J. Scamp ; James G. Jirak ; Nicholas S. Dolan ; Ilia A. Guzei ; Jennifer M. Schomaker
• 刊名：Organic Letters
• 出版年：2016
• 出版时间：June 17, 2016
• 年：2016
• 卷：18
• 期：12
• 页码：3014-3017
• 全文大小：395K
• 年卷期：0
• ISSN：1523-7052

文摘

The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon–hydrogen (C–H) bond amination of activated secondary C–H bonds over tertiary alkyl C(sp³)–H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py₅Me₂)AgOTf]₂, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C–H bonds over tertiary alkyl C(sp³)–H bonds.