Zf. Xi et al., HIGHLY SELECTIVE AND PRACTICAL ALKYNE-ALKYNE CROSS-COUPLING USING CP(2)ZRBU(2) AND ETHYLENE, Journal of organic chemistry, 60(14), 1995, pp. 4444-4448
Highly selective alkyne-alkyne cross coupling reactions were achieved
using Cp(2)ZrBu(2) and ethylene gas. First, alkynes were treated with
1.2 equiv of Cp(2)ZrBu(2) (Negishi reagent) under ethylene gas to give
zirconacyclopentenes with high selectivities. Subsequent addition of
a second alkyne to the solution of zirconacyclopentenes at 50 degrees
C gave unsymmetrical zirconacyclopentadienes selectively. After hydrol
ysis unsymmetrical dienes were obtained in high yields.