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Synthesis 2010(14): 2475-2489  
DOI: 10.1055/s-0029-1218809
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

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

Shin Kamijo, Yuuki Amaoka, Masayuki Inoue*
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Fax: +81(3)58410568; e-Mail: inoue@mol.f.u-tokyo.ac.jp;
Further Information

Publication History

Received 28 April 2010
Publication Date:
02 June 2010 (online)

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Abstract

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 sp³ 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.

Key words

catalysis - oxidation - ethers - alcohols - ketones - carboxylic acids

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5

See reference 1b, pp 231-236 (MnO2) and pp 311-317 (KMnO4).

18

The addition of a small amount of water during preparation of the Mn catalyst helped to give reproducible results. Water dissolves the MnCl2 salt and promotes the formation of the Mn catalyst.

19

Over-oxidation took place to produce cyclodocecane-1,5-dione as a byproduct (<5% yield).

20

See the experimental section for details.

22

Because methine C-H bonds have a higher intrinsic reactivity toward oxidation than do methylene C-H bonds, and no formation of octanoate ester was observed, we assumed that octanoic acid was generated through intermediate A; however, we cannot rule out the possibility of the involvement of intermediate B.

26

For pioneering works on benzylic C-H oxidation with a Mn/terpy catalyst and tetrabutylammonium Oxone (TBA-Oxone), see reference 14.

27

A stock solution of the premixed manganese complex in acetonitrile can be used.

31

The reaction in the absence of the Mn catalyst gave no oxidized product 2a, and quantitative recovery of alcohol 5a was observed. This result eliminates the possibility that dioxirane is formed from acetone under the reaction conditions.

32

Treatment of an olefin with the Mn catalyst/KHSO5 system resulted in clean formation of an epoxide (Scheme  [6] ).

Scheme 6 Formation of an epoxide from an olefin