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Unified Oxidation Protocol for the Synthesis of Carbonyl Compounds Using a Manganese Catalyst

  作者 KAMIJO SHIN; AMAOKA YUUKI; INOUE MASAYUKI  
  选自 期刊  Synthesis;  卷期  2010年-14;  页码  2475-2489  
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[摘要]We have developed a unified protocol for the oxidation of ethers, benzylic compounds, and alcohols to carbonyl compounds. The protocol uses catalytic amounts of manganese(II) chloride tetrahydrate and 4,4',4 ''-tri(t-butyl)-2,2':6',2 ''-terpyridine in combination with a stoichiometric amount of either m-chloroperbenzoic acid (MCPBA) or potassium hydrogen peroxysulfate (KHSO5). A reagent system consisting of the Mn catalyst and MCPBA permitted the chemoselective sp(3) C-H oxidation of alkyl ethers and benzylic compounds to generate the corresponding ketones. Alternatively, the water-soluble inorganic salt KHSO5 in combination with the Mn catalyst was used to oxidize alcohols to ketones or carboxylic acids. Importantly, the Mn catalyst/KHSO5 system eliminates technical difficulties associated with the isolation of carboxylic acid products. All the oxidations presented in this feature article proceed at sub-ambient temperature in an aerobic atmosphere, and can therefore be used in practical syntheses of complex organic molecules.

 
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