Beyond the Dimer and Trimer: Tetraspiro[2.1.25.1.29.1.213.13] hexadecane‐1,3,5,7‐tetraone—the Cyclic Tetramer of Carbonylcyclopropane |
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| Authors: | Dr. Kseniya N. Sedenkova Dr. Elena B. Averina Dr. Yuri K. Grishin Kristian S. Andriasov Svetlana A. Stepanova Dr. Vitaly A. Roznyatovsky Prof. Andrei G. Kutateladze Dr. Victor B. Rybakov Dr. Dmitry V. Albov Dr. Tamara S. Kuznetsova Prof. Nikolay S. Zefirov |
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| Affiliation: | 1. Department of Chemistry, Lomonosov Moscow State University, Moscow, Russian Federation;2. N.D. Zelinsky Institute of Organic Chemistry RAS, Moscow, Russian Federation;3. Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado, USA |
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| Abstract: | Tetraspiro[2.1.25.1.29.1.213.13]hexadecane‐1,3,5,7‐tetraone 4 , a unique tetraketone containing a cyclooctane core and four spiroannelated cyclopropane moieties, represents the previously unknown cyclotetramer of carbonylcyclopropane. For this purpose oxidation of the parent polyspirocyclic hydrocarbon was examined under various oxidative conditions, and the reactivity of oxidants towards methylene groups of the eight‐membered cycle, activated by adjacent spirocyclopropane rings, was evaluated and contrasted. Whereas the treatment of tetraspirohexadecane with ozone resulted in monooxidation, its reaction with methyl(trifluoromethyl)dioxirane afforded the product of four‐fold oxidation, triketoalcohol 10 . Subsequent oxidation of the latter with Dess–Martin periodinane gave the target tetraketone 4 . |
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| Keywords: | ketones oxidation oxygenation polycycles small ring systems |
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