Ir-Catalyzed Intermolecular Branch-Selective Allylic C-H Amidation of Unactivated Terminal Olefins
Ir-Catalyzed Intermolecular Branch-Selective Allylic C-H Amidation of Unactivated Terminal Olefins
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DOI：
10.1021/jacs.9b00237
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发表时间：
2019-02-13
影响因子：
15
通讯作者：
Rovis, Tomislav
中科院分区：
文献类型：
--
作者：
Lei, Honghui;Rovis, Tomislav
在Ir（III）催化下，实现了分子间支链选择性烯丙基C-H酰胺化反应。该反应进行通过初始烯丙基C-H活化，支持的分离和晶体学表征的烯丙基-铱（III）中间体，随后通过随后的氧化酰胺化与容易获得的二恶唑酮作为nitrenoid前体。各种酰胺以良好的产率和区域选择性被成功地安装在末端烯烃的支化位置上。重要的是，该反应允许使用酰胺衍生的类氮杂环戊烯前体，避免了有问题的Curtius型重排。
An efficient method for intermolecular branch-selective allylic C-H amidation has been accomplished via Ir(III) catalysis. The reaction proceeds through initial allylic C-H activation, supported by the isolation and crystallographic characterization of an allyl-Ir(III) intermediate, followed by a subsequent oxidative amidation with readily available dioxazolones as nitrenoid precursors. A diverse range of amides are successfully installed at the branched position of terminal alkenes in good yields and regioselectivities. Importantly, the reaction allows the use of amide-derived nitrenoid precursors avoiding problematic Curtius-type rearrangements.