Mechanism and Scope of the MnIII-Initiated Oxidation of β-Ketocarbonyl Compounds: Furan Synthesis

Authors

  • Chao Wang,

    1. School of Pharmacy, East China University of Science and Technology, Meilong Road 130, Shanghai, 20037, China
    2. Department of Nano Science and Engineering; Department of Chemistry, Myong Ji University, San 38-2, Nam-Dong, Yongin, Kyunggi-Do, 449–728, South Korea, Fax: +82-31-335-7248, http://www.kooslab.org
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  • Zhilong Li,

    1. School of Pharmacy, East China University of Science and Technology, Meilong Road 130, Shanghai, 20037, China
    2. Department of Nano Science and Engineering; Department of Chemistry, Myong Ji University, San 38-2, Nam-Dong, Yongin, Kyunggi-Do, 449–728, South Korea, Fax: +82-31-335-7248, http://www.kooslab.org
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  • Yeming Ju,

    1. School of Pharmacy, East China University of Science and Technology, Meilong Road 130, Shanghai, 20037, China
    2. Department of Nano Science and Engineering; Department of Chemistry, Myong Ji University, San 38-2, Nam-Dong, Yongin, Kyunggi-Do, 449–728, South Korea, Fax: +82-31-335-7248, http://www.kooslab.org
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  • Sangho Koo

    1. School of Pharmacy, East China University of Science and Technology, Meilong Road 130, Shanghai, 20037, China
    2. Department of Nano Science and Engineering; Department of Chemistry, Myong Ji University, San 38-2, Nam-Dong, Yongin, Kyunggi-Do, 449–728, South Korea, Fax: +82-31-335-7248, http://www.kooslab.org
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  • Dedication to Professor Masato Koreeda on the occasion of his 70th birthday

Abstract

Unless the MnIII-produced carbon-radical from β-ketocarbonyl compounds undergoes smooth intramolecular addition to alkenes, it traps molecular oxygen in the reaction medium to produce a peroxy radical, which reacts with the neighbouring carbonyl group to form 1,2-dioxetane. Thermal decomposition of 1,2-dioxetane completes the oxidation to produce α-oxo ester. This oxidation seems to be general at 50 °C under aerobic conditions, and can be catalytic for MnIII in AcOH with ultrasonic irradiation. Thus, the development of a new synthetic method for diversely substituted furans has been accomplished based on a couple of the MnIII-initiated domino oxidation of β-ketocarbonyl compounds with a suitable α-allylic substitution.

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