jo6b02540_si_002.cif (79.08 kB)
Download fileCobalt-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
dataset
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. DzhemilevA 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.