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Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide

Title
Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide
Authors
Miao, ChengxiaLi, Xiao-XiLee, Yong-MinXia, ChunguWang, YongNam, WonwooSun, Wei
Ewha Authors
남원우
SCOPUS Author ID
남원우scopus
Issue Date
2017
Journal Title
CHEMICAL SCIENCE
ISSN
2041-6520JCR Link2041-6539JCR Link
Citation
vol. 8, no. 11, pp. 7476 - 7482
Publisher
ROYAL SOC CHEMISTRY
Indexed
SCI; SCIE; SCOPUS WOS
Abstract
The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an alpha-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn-oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the alpha-CH bonds of R- and S-enantiomers by a chiral high-valent manganese-oxo complex, supporting the experimental result from the OKR of secondary alcohols.
DOI
10.1039/c7sc00891k
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자연과학대학 > 화학·나노과학전공 > Journal papers
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