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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.
J Org Chem. 2017 01 06; 82(1):471-480.JO

Abstract

A new, effective catalytic system based on Co(acac)2 has 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.

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Publisher Full Text (DOI)

Authors+Show Affiliations

D'yakonov VA
Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis of RAS (IPC RAS) , Prospect Octyabrya, 141, 450075 Ufa, Russian Federation.
Kadikova GN
Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis of RAS (IPC RAS) , Prospect Octyabrya, 141, 450075 Ufa, Russian Federation.
Dzhemileva LU
Department of Immunology and Human Reproductive Health, Bashkir State Medical University , Lenin Street, 3, 450003 Ufa, Russian Federation.
Gazizullina GF
Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis of RAS (IPC RAS) , Prospect Octyabrya, 141, 450075 Ufa, Russian Federation.
Ramazanov IR
Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis of RAS (IPC RAS) , Prospect Octyabrya, 141, 450075 Ufa, Russian Federation.
Dzhemilev UM
Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis of RAS (IPC RAS) , Prospect Octyabrya, 141, 450075 Ufa, Russian Federation.

MeSH

AlkynesBridged Bicyclo CompoundsCatalysisCobaltCycloaddition ReactionCyclooctanesMolecular Structure

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

27935701

Citation

D'yakonov, Vladimir A., et al. "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." The Journal of Organic Chemistry, vol. 82, no. 1, 2017, pp. 471-480.
D'yakonov VA, Kadikova GN, Dzhemileva LU, et al. 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. J Org Chem. 2017;82(1):471-480.
D'yakonov, V. A., Kadikova, G. N., Dzhemileva, L. U., Gazizullina, G. F., Ramazanov, I. R., & Dzhemilev, U. M. (2017). 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. The Journal of Organic Chemistry, 82(1), 471-480. https://doi.org/10.1021/acs.joc.6b02540
D'yakonov VA, et al. 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. J Org Chem. 2017 01 6;82(1):471-480. PubMed PMID: 27935701.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - 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. AU - D'yakonov,Vladimir A, AU - Kadikova,Gulnara N, AU - Dzhemileva,Lilya U, AU - Gazizullina,Guzel F, AU - Ramazanov,Ilfir R, AU - Dzhemilev,Usein M, Y1 - 2016/12/20/ PY - 2016/12/10/pubmed PY - 2018/6/13/medline PY - 2016/12/10/entrez SP - 471 EP - 480 JF - The Journal of organic chemistry JO - J Org Chem VL - 82 IS - 1 N2 - A new, effective catalytic system based on Co(acac)2 has 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. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/27935701/Cobalt_Catalyzed_[6_+_2]_Cycloaddition_of_Alkynes_with_1357_Cyclooctatetraene_as_a_Key_Element_in_the_Direct_Construction_of_Substituted_Bicyclo[4_3_1]decanes_ DB - PRIME DP - Unbound Medicine ER -