title: Highly Enantioselective Iron-Catalyzed cis-Dihydroxylation of Alkenes with Hydrogen Peroxide Oxidant via an Fe(III) -OOH Reactive Intermediate.
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 [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 H2 O2 as an oxidant and alkenes in a limiting amount. This "[Fe(II) (L)(OTf)2 ]+H2 O2 " method is applicable to both (E)-alkenes and terminal alkenes (24 examples >80 % ee, up to 1 g scale). Mechanistic studies, including (18) O-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.
authors.affiliation: Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, 354 Feng Lin Road, Shanghai, China.
authors.forename: Chao
authors.initials: C
authors.lastname: Zang
authors.affiliation: Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China.
authors.forename: Yungen
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, 354 Feng Lin Road, Shanghai, China.
authors.forename: Zhen-Jiang
authors.initials: ZJ
authors.lastname: Xu
authors.affiliation: Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China.
authors.forename: Chun-Wai
authors.initials: CW
authors.lastname: Tse
authors.affiliation: Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China.
authors.forename: Xiangguo
authors.initials: X
authors.lastname: Guan
authors.affiliation: Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China.
authors.forename: Jinhu
authors.initials: J
authors.lastname: Wei
authors.affiliation: Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China.
authors.forename: Jie-Sheng
authors.initials: JS
authors.lastname: Huang
authors.affiliation: Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, 354 Feng Lin Road, Shanghai, China. cmche@hku.hk.|Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China. cmche@hku.hk.
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Che
keywords: DFT calculations; N-ligands; asymmetric catalysis; cis-dihydroxylation; iron catalysis