title: Beyond the Dimer and Trimer: Tetraspiro[2.1.2(5).1.2(9).1.2(13).1(3)] hexadecane-1,3,5,7-tetraone--the Cyclic Tetramer of Carbonylcyclopropane.
abstract: Tetraspiro[2.1.2(5).1.2(9).1.2(13).1(3)]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.
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1-3, Moscow, Russian Federation.|N.D. Zelinsky Institute of Organic Chemistry RAS, 119991, Leninsky Prospect, 47, Moscow, Russian Federation.
authors.forename: Kseniya N
authors.initials: KN
authors.lastname: Sedenkova
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1-3, Moscow, Russian Federation. elaver@org.chem.msu.ru.|N.D. Zelinsky Institute of Organic Chemistry RAS, 119991, Leninsky Prospect, 47, Moscow, Russian Federation. elaver@org.chem.msu.ru.
authors.forename: Elena B
authors.initials: EB
authors.lastname: Averina
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1-3, Moscow, Russian Federation.
authors.forename: Yuri K
authors.initials: YK
authors.lastname: Grishin
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1-3, Moscow, Russian Federation.
authors.forename: Kristian S
authors.initials: KS
authors.lastname: Andriasov
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1-3, Moscow, Russian Federation.
authors.forename: Svetlana A
authors.initials: SA
authors.lastname: Stepanova
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1-3, Moscow, Russian Federation.
authors.forename: Vitaly A
authors.initials: VA
authors.lastname: Roznyatovsky
authors.affiliation: Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado, 80208, USA. akutatel@du.edu.
authors.forename: Andrei G
authors.initials: AG
authors.lastname: Kutateladze
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1-3, Moscow, Russian Federation.
authors.forename: Victor B
authors.initials: VB
authors.lastname: Rybakov
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1-3, Moscow, Russian Federation.
authors.forename: Dmitry V
authors.initials: DV
authors.lastname: Albov
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1-3, Moscow, Russian Federation.
authors.forename: Tamara S
authors.initials: TS
authors.lastname: Kuznetsova
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1-3, Moscow, Russian Federation.
authors.forename: Nikolay S
authors.initials: NS
authors.lastname: Zefirov
keywords: ketones; oxidation; oxygenation; polycycles; small ring systems