Highly Enantioselective Iron-Catalyzed cis-Dihydroxylation of Alkenes with Hydrogen Peroxide Oxidant via an FeIII-OOH Reactive Intermediate

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• 作者：Dr. Chao Zang ; Dr. Yungen Liu ; Dr. Zhen-Jiang Xu ; Chun-Wai Tse ; Dr. Xiangguo Guan ; Jinhu Wei ; Dr. Jie-Sheng Huang and Prof. Dr. Chi-Ming Che
• 刊名：Angewandte Chemie
• 出版年：2016
• 出版时间：August 22, 2016
• 年：2016
• 卷：128
• 期：35
• 页码：10409-10413
• 全文大小：1246K
• ISSN：1521-3757

文摘

The development of environmentally benign catalysts for highly enantioselective asymmetric cis-dihydroxylation (AD) of alkenes with broad substrate scope remains a challenge. By employing [Fe^II(L)(OTf)₂] (L=N,N′-dimethyl-N,N′-bis(2-methyl-8-quinolyl)-cyclohexane-1,2-diamine) as a catalyst, cis-diols in up to 99.8 % ee with 85 % isolated yield have been achieved in AD of alkenes with H₂O₂ as an oxidant and alkenes in a limiting amount. This “[Fe^II(L)(OTf)₂]+H₂O₂” method is applicable to both (E)-alkenes and terminal alkenes (24 examples >80 % ee, up to 1 g scale). Mechanistic studies, including ¹⁸O-labeling, UV/Vis, EPR, ESI-MS analyses, and DFT calculations lend evidence for the involvement of chiral Fe^III-OOH active species in enantioselective formation of the two C−O bonds.