协同双导向基团促进的铑(III)催化与环丙基醇的对映选择性 C-H 环丙烷化反应。
Synergistic Dual Directing Groups-Enabled Diastereoselective C-H Cyclopropylation via Rh(III)-Catalyzed Couplings with Cyclopropenyl Alcohols.
机构信息
Guangzhou Municipal and Guangdong Provincial Key Laboratory of Protein Modification and Degradation & Molecular Target and Clinical Pharmacology, State Key Laboratory of Respiratory Disease, School of Pharmaceutical Sciences and Fifth Affiliated Hospital , Guangzhou Medical University , Guangzhou , Guangdong 511436 , China.
出版信息
Org Lett. 2020 Feb 21;22(4):1295-1300. doi: 10.1021/acs.orglett.9b04608. Epub 2020 Feb 4.
By using a synergistic dual directing group-assisted C-H activation strategy and simply modifying the reaction conditions, we realized a robust and general Cp*Rh(III)-catalyzed C-H cyclopropylation of -acetoxybenzamides with cyclopropenyl alcohols, providing regio-, chemo-, and diastereoselective access to - and -1,1-dimethylcyclopropane-functionalized benzamides in a redox-neutral and controllable manner. Experimental and density functional theory studies clarify the roles of the NH-OAc and OH groups and deduce two distinct Rh(III)-Rh(V)-Rh(III) pathways for presenting such selectivity.
通过使用协同双导向基辅助 C-H 活化策略，并简单地修改反应条件，我们实现了 -乙酰氧基苯甲酰胺与环丙烯醇的稳定且通用的 Cp*Rh(III)催化 C-H 环丙基化反应，以氧化还原中性和可控的方式提供了区域选择性、化学选择性和非对映选择性的 -和-1,1-二甲基环丙基化苯甲酰胺。实验和密度泛函理论研究阐明了 NH-OAc 和 OH 基团的作用，并推导出了两种不同的 Rh(III)-Rh(V)-Rh(III)途径来呈现这种选择性。
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