Gg. Melikyan et al., A NOVEL SYNTHETIC APPROACH TO CYCLOOCTA-1,5-DIYNES AND CYCLOOCT-3-ENE-1,5-DIYNES VIA COBALT-COMPLEXED PROPARGYL RADICALS, Organometallics, 14(5), 1995, pp. 2170-2172
A novel synthetic strategy has been elaborated to produce Co-2(CO)(6)-
complexed 1,5-cyclooctadiynes and the first cyclooct-3-ene-1,5-diyne d
erivative. Eight-membered rings are formed with high dl-diastereoselec
tivity (de greater than or equal to 98%) by reduction of the correspon
ding propargyl dication complexes under hetero- (Zn) and homogeneous (
Na/Ph(2)CO) conditions. A novel ''red-ox'' decomplexation method has b
een developed for 1,5-cyclooctadiynes.