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Highly Enantioselective Oxidation of Spirocyclic Hydrocarbons by Bioinspired Manganese Catalysts and Hydrogen Peroxide

Title
Highly Enantioselective Oxidation of Spirocyclic Hydrocarbons by Bioinspired Manganese Catalysts and Hydrogen Peroxide
Authors
Qu, BinXu, DaqianSun, QiangshengMiao, ChengxiaLee, Yong-MinLi, Xiao-XiNam, WonwooSun, Wei
Ewha Authors
남원우
SCOPUS Author ID
남원우scopus
Issue Date
2018
Journal Title
ACS CATALYSIS
ISSN
2155-5435JCR Link
Citation
ACS CATALYSIS vol. 8, no. 3, pp. 2479 - 2487
Keywords
C-H oxidationmanganese catalystasymmetric oxidationhydrogen peroxidemechanismmanganese-oxo
Publisher
AMER CHEMICAL SOC
Indexed
SCIE; SCOPUS WOS scopus
Document Type
Article
Abstract
Bioinspired manganese complexes have emerged as attractive catalysts for a number of selective oxidation reactions over the past several decades. In the present study, we report the enantioselective oxidation of spirocyclic compounds with manganese complexes bearing tetradentate N4 ligands as catalysts and aqueous H2O2 as a terminal oxidant under mild conditions; spirocyclic tetralone (1a) and its derivatives bearing electron-donating and -withdrawing substituents are converted to their corresponding chiral spirocyclic beta,beta'-diketones with high yields and enantioselectivities. Spirocyclic indanones are also converted to the beta,beta'-spirobiindanones with high enantioselectivities. Indeed, the reaction expands the diversity of chiral spirocyclic diketones via a late-stage oxidative process. In addition, it is of importance to note that the catalytic reaction can be easily scaled up and the chiral spirocyclic beta,beta'-diketones can be transformed into diol products. In mechanistic studies, we have shown that (1) ketones were yielded as products via the initial formation of alcohols, followed by the further oxidation of the alcohols to ketones, (2) hydrogen atom (H atom) abstraction from the methylene C-H bonds of 1a by a putative Mn(V)-oxo intermediate was proposed to be the rate-determining step, and (3) the C-H bond hydroxylation of 1a by the Mn(V)-oxo species was proposed to occur via oxygen rebound mechanism. On the basis of these results, we have proposed a plausible mechanism for the selective C-H bond oxidation of hydrocarbons by bioinspired manganese catalysts and hydrogen peroxide.
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DOI
10.1021/acscatal.7b03601
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자연과학대학 > 화학·나노과학전공 > Journal papers
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