title: Cobalt-Catalyzed [6 + 2] Cycloaddition of Alkynes with 1,3,5,7-Cyclooctatetraene as a Key Element in the Direct Construction of Substituted Bicyclo[4.3.1]decanes.
abstract: A new, effective catalytic system based on Co(acac)2has been developed for [6 + 2] cycloaddition of terminal alkynes to 1,3,5,7-cyclooctatetraene to give substituted bicyclo[4.2.2]deca-2,4,7,9-tetraenes in high yields (68-85%). The electrophilic activation of double bonds in the bicyclic products with m-CPBA is an efficient method for the synthesis of substituted bicyclo[4.3.1]deca-2,4,8-triene-7,10-diols, which form the key structural moieties of numerous natural biologically active compounds. The structures of the obtained compounds were reliably proven by modern spectral methods and X-ray diffraction. The mechanism of the discovered rearrangement was studied both using deuterium-labeled bicyclo[4.2.2]deca-2,4,7,9-tetraenes and utilizing quantum chemical calculations. The obtained substituted bicyclo[4.3.1]deca-2,4,8-triene-7,10-diols and their keto derivatives showed high antitumor activity in vitro against Hek293, Jurkat, K562, and A549 tumor cell lines.
authors.affiliation: Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis of RAS (IPC RAS) , Prospect Octyabrya, 141, 450075 Ufa, Russian Federation.
authors.forename: Vladimir A
authors.identifier: 0000-0002-7787-5054
authors.initials: VA
authors.lastname: D'yakonov
authors.affiliation: Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis of RAS (IPC RAS) , Prospect Octyabrya, 141, 450075 Ufa, Russian Federation.
authors.forename: Gulnara N
authors.initials: GN
authors.lastname: Kadikova
authors.affiliation: Department of Immunology and Human Reproductive Health, Bashkir State Medical University , Lenin Street, 3, 450003 Ufa, Russian Federation.
authors.forename: Lilya U
authors.initials: LU
authors.lastname: Dzhemileva
authors.affiliation: Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis of RAS (IPC RAS) , Prospect Octyabrya, 141, 450075 Ufa, Russian Federation.
authors.forename: Guzel F
authors.initials: GF
authors.lastname: Gazizullina
authors.affiliation: Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis of RAS (IPC RAS) , Prospect Octyabrya, 141, 450075 Ufa, Russian Federation.
authors.forename: Ilfir R
authors.initials: IR
authors.lastname: Ramazanov
authors.affiliation: Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis of RAS (IPC RAS) , Prospect Octyabrya, 141, 450075 Ufa, Russian Federation.
authors.forename: Usein M
authors.initials: UM
authors.lastname: Dzhemilev
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003035:Cobalt / Q000737:chemistry*; D061565:Cycloaddition Reaction; D034242:Cyclooctanes / Q000737:chemistry*; D015394:Molecular Structure
chemical_list: D000480:Alkynes; D001643:Bridged Bicyclo Compounds; D034242:Cyclooctanes; D003035:Cobalt; C534209:1,3,5,7-cyclooctatetraene