Highly Enantioselective Iron‐Catalyzed cis‐Dihydroxylation of Alkenes with Hydrogen Peroxide Oxidant via an FeIII‐OOH Reactive Intermediate |
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| Authors: | Dr Chao Zang Dr Yungen Liu Dr Zhen‐Jiang Xu Chun‐Wai Tse Dr Xiangguo Guan Jinhu Wei Dr Jie‐Sheng Huang Prof?Dr Chi‐Ming Che |
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| Institution: | 1. Shanghai–Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Shanghai, China;2. Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Hong Kong, China |
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| Abstract: | The development of environmentally benign catalysts for highly enantioselective asymmetric cis‐dihydroxylation (AD) of alkenes with broad substrate scope remains a challenge. By employing FeII(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 “FeII(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 FeIII‐OOH active species in enantioselective formation of the two C?O bonds. |
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| Keywords: | asymmetric catalysis cis-dihydroxylation DFT calculations iron catalysis N-ligands |
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