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

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....

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Bibliographic Details
Published in:Chemical science (Cambridge) 2017-11, Vol.8 (11), p.7476-7482
Main Authors: Miao, Chengxia, Li, Xiao-Xi, Lee, Yong-Min, Xia, Chungu, Wang, Yong, Nam, Wonwoo, Sun, Wei
Format: Article
Language:English
Subjects:
Alcohol
Alcohols
Catalysis
Catalytic oxidation
Density functional theory
Enantiomers
Hydrogen peroxide
Manganese
Oxidation
Substrates
Sulfuric acid
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Summary: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 hydrogen atom (H-atom) abstraction from an α-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 α-CH bonds of - and -enantiomers by a chiral high-valent manganese-oxo complex, supporting the experimental result from the OKR of secondary alcohols.
ISSN:2041-6520
2041-6539
DOI:10.1039/c7sc00891k