Cyclobutenes by platinum-catalyzed cycloisomerization reactions of enynes.
1,6-Enynes bearing (electron-rich) aryl substituents on their alkyne moiety rearrange to cyclobutene derivatives in the presence of catalytic amounts of PtCl2 in toluene. The reaction is significantly accelerated when performed under an atmosphere of CO (1 atm), most likely by increasing the electrophilicity of the metal template by temporary coordination to this pi-acidic ligand. This transformation allows the build up of considerable strain in the products as witnessed by the productive formation of tricyclic skeletons, such as 7 or 9. Moreover, these products provide evidence for the mechanistic scenario of platinum-catalyzed cycloisomerization reactions previously proposed, which are thought to proceed via organo-platinum species that mimic the reactivity of metal-complexed "nonclassical" carbocations.
Fürstner
Alois
A
Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim/Ruhr, Germany. fuerstner@mpi-muelheim.mpg.de
Davies
Paul W
PW
Gress
Tobias
T