Department of Chemistry , Columbia University , New York , New York 10027 , United States.
J Am Chem Soc. 2019 Feb 13;141(6):2268-2273. doi: 10.1021/jacs.9b00237. Epub 2019 Feb 4.
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.
通过铱(III)催化，实现了一种有效的分子间支链选择性烯丙基 C-H 酰胺化方法。该反应通过初始烯丙基 C-H 活化进行，得到的烯丙基-Ir(III)中间体经分离和晶体学表征得到支持，随后与易得的二恶唑酮作为氮烯前体进行后续的氧化酰胺化。各种酰胺成功地在末端烯烃的支链位置以良好的收率和区域选择性进行了安装。重要的是，该反应允许使用酰胺衍生的氮烯前体，避免了有问题的Curtius 重排。
