Highly EnantioselectiveIron-Catalyzed cis-Dihydroxylation ofAlkenes with Hydrogen Peroxide Oxidant via an FeIII-OOH ReactiveIntermediate
Chao Zang+, Yungen Liu+, Zhen-Jiang Xu, Chun-Wai Tse, Xiangguo Guan, Jinhu Wei, Jie-
Sheng Huang, and Chi-Ming Che*
[*] Dr. C. Zang,[+] Dr. Z.-J. Xu, Prof. Dr. C.-M. Che
Shanghai–Hong Kong Joint Laboratory in Chemical Synthesis
Shanghai Institute of Organic Chemistry
354 Feng Lin Road, Shanghai (China)
E-mail: cmche@hku.hk
Dr. Y. Liu,[+] C.-W. Tse, Dr. X. Guan, J. Wei, Dr. J.-S. Huang,
Prof. Dr. C.-M. Che
Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong
Pokfulam Road, Hong Kong (China)
[+] These authors contributed equally to this work.
http://onlinelibrary.wiley.com/doi/10.1002/anie.201603410/abstract
354 Feng Lin Road, Shanghai (China)
E-mail: cmche@hku.hk
Dr. Y. Liu,[+] C.-W. Tse, Dr. X. Guan, J. Wei, Dr. J.-S. Huang,
Prof. Dr. C.-M. Che
Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong
Pokfulam Road, Hong Kong (China)
[+] These authors contributed equally to this work.
http://onlinelibrary.wiley.com/doi/10.1002/anie.201603410/abstract
Abstract
The development of environmentally benign cata- lysts for highly enantioselective asymmetric cis-dihydroxyla- tion (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-dia- mine) 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 CO bonds.
The development of environmentally benign cata- lysts for highly enantioselective asymmetric cis-dihydroxyla- tion (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-dia- mine) 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 CO bonds.
コメント