A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds.
A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds.
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DOI：
10.1021/acs.orglett.6b01392
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发表时间：
2016-05
期刊：
影响因子：
5.2
通讯作者：
Ryan J. Scamp;James G. Jirak;Nicholas S. Dolan;I. Guzei;J. Schomaker
中科院分区：
文献类型：
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作者：
Ryan J. Scamp;James G. Jirak;Nicholas S. Dolan;I. Guzei;J. Schomaker
能够促进活化的仲C-H键相对于叔烷基C（sp（3））-H键的一般的、催化剂控制的和选择性的碳-氢（C-H）键胺化的过渡金属络合物的发现具有挑战性，因为当涉及反应性氮烯中间体时，底物控制通常占主导地位。在这封信中，我们报告了一个新的银配合物，[（Py 5 Me 2）AgOTf]2的设计，显示一般和良好到优秀的选择性氮烯插入到炔丙基，苄基，烯丙基C-H键叔烷基C（sp（3））-H键。
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(sp(3))-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(sp(3))-H bonds.