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. 2017 Nov 1;8(11):7476-7482.
doi: 10.1039/c7sc00891k. Epub 2017 Sep 7.

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

Chengxia Miao  1   2 , Xiao-Xi Li  1   3 , Yong-Min Lee  3 , Chungu Xia  1 , Yong Wang  1 , Wonwoo Nam  1   3 , Wei Sun  1
Affiliations

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

Chengxia Miao et al. Chem Sci. .

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 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 R- and S-enantiomers by a chiral high-valent manganese-oxo complex, supporting the experimental result from the OKR of secondary alcohols.

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Figures

Scheme 1
Scheme 1. (A) Schematic structures of manganese complexes bearing N4 ligands: MnII(P-MCP)(OTf)2 (1; P-MCP = (1R,2R)-N,N′-dimethyl-N,N′-bis-(phenyl-2-pyridinylmethyl)cyclohexane-1,2-diamine and OTf– = CF3SO3 –), MnII(Dpb-MCP)(OTf)2 (2; Dbp-MCP = (1R,2R)-N,N′-di-methyl-N,N′-bis((R)-(3,5-di-tert-butylphenyl)-2-pyridinylmethyl)cyclohexane-1,2-diamine) and MnII(MCP)(OTf)2 (3; MCP = (1R,2R)-N,N′-dimethyl-N,N′-bis(2-pyridinylmethyl)cyclohexane-1,2-diamine). (B) Summary of the alcohol oxidation reaction. (C) Summary of the oxidative kinetic resolution (OKR) of secondary alcohols.
Fig. 1
Fig. 1. Plots of the conversion yields (black triangles) of 1-phenylethanol and the ee values (red circles) of unreacted 1-phenylethanol against the number of equivalents of H2O2 obtained in the catalytic oxidation of 1-phenylethanol (0.50 mmol) by 2 (0.20 mol%) and H2O2 (0–1.0 equiv. based on the concentration of the substrate) in the presence of H2SO4 (1.0 mol%) in CH3CN at 0 °C for 1 h.
Fig. 2
Fig. 2. Hammett plot of log k rel against the Hammett parameter (σ) for the catalytic oxidation of para-substituted benzyl alcohols by 1 (0.30 mol%) with H2O2 (0.40 equiv. based on the concentration of the substrate) as an oxidant in the presence of H2SO4 (0.30 mol%) in CH3CN at 25 °C.
Scheme 2
Scheme 2. Oxidation of cyclobutanol to cyclobutanone.
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