American Chemical Society
jo6b02540_si_002.cif (79.08 kB)

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

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Version 2 2016-12-20, 21:30
Version 1 2016-12-20, 12:48
posted on 2016-12-09, 00:00 authored by Vladimir A. D’yakonov, Gulnara N. Kadikova, Lilya U. Dzhemileva, Guzel F. Gazizullina, Ilfir R. Ramazanov, Usein M. Dzhemilev
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.