title: symm-Tetramethylenecyclooctane: en route to polyspirocycles.
abstract: A straightforward gram-scale synthesis of 1,3,5,7-tetrakis(methylidene)cyclooctane (TMCO) from commercial adamantane-1,3-dicarboxylic acid has been developed. TMCO exhibits high reactivity toward a number of carbenes and epoxidizing reagents, undergoing multiple cyclopropanations, dihalocyclopropanations, or epoxidations of four double bonds to yield polyspirocyclic products. Stereochemical features of polyspirocyclopropanated compounds have been thoroughly examined in experimental (NMR) and theoretical (DFT) studies. Comprehensive stereochemical assignment of TMCO adducts with dihalocarbenes and spiroepoxy products was achieved. The conditions of the formation of 1-methyl-3,7-bis(methylidene)bicyclo[3.3.1]nonane from the adamantane derivative were optimized, and diadducts of this diene with dihalocarbenes were isolated and characterized.
authors.affiliation: Department of Chemistry, Lomonosov Moscow State University , Leninskie Gory, 1-3, Moscow 119991, Russia.
authors.forename: Elena B
authors.initials: EB
authors.lastname: Averina
authors.forename: Kseniya N
authors.initials: KN
authors.lastname: Sedenkova
authors.forename: Stanislav G
authors.initials: SG
authors.lastname: Bakhtin
authors.forename: Yuri K
authors.initials: YK
authors.lastname: Grishin
authors.forename: Andrei G
authors.initials: AG
authors.lastname: Kutateladze
authors.forename: Vitaly A
authors.initials: VA
authors.lastname: Roznyatovsky
authors.forename: Victor B
authors.initials: VB
authors.lastname: Rybakov
authors.forename: Gennady M
authors.initials: GM
authors.lastname: Butov
authors.forename: Tamara S
authors.initials: TS
authors.lastname: Kuznetsova
authors.forename: Nikolay S
authors.initials: NS
authors.lastname: Zefirov
mesh_terms: D000218:Adamantane / Q000031:analogs & derivatives* / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D034242:Cyclooctanes / Q000138:chemical synthesis* / Q000737:chemistry; D003998:Dicarboxylic Acids / Q000737:chemistry*; D007202:Indicators and Reagents / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D011789:Quantum Theory; D013141:Spiro Compounds / Q000737:chemistry*
chemical_list: C000599812:1,3,5,7-tetrakis(methylidene)cyclooctane; C421745:1,3-adamantanedicarboxylic acid; C000599814:1-methyl-3,7-bis(methylidene)bicyclo(3.3.1)nonane; D001643:Bridged Bicyclo Compounds; D034242:Cyclooctanes; D003998:Dicarboxylic Acids; D007202:Indicators and Reagents; D013141:Spiro Compounds; D000218:Adamantane