Gold-catalyzed cyclizations of 1,6-diynes.
New gold-catalyzed cyclization reactions of 1,6-diynes (2,2-dipropargylmalonates) are reported. Symmetrically (Me, Et) and unsymmetrically disubstituted (Me, Et, Ph) 1,6-diynes provided stereoselectively the Z-cyclopentylidene derivatives in 31-60% and 49-83% yield, respectively. High regioselectivity (97:3) was obtained for the cyclization of Me/Ph-substituted 1,6-diynes. A monosubstituted terminal diyne afforded a cyclopentene derivative (2-acetyl-3-alkylcyclopent-2-ene-1,1-dicarboxylate, 43%), while the diterminal 1,6-diyne (2,2-di(prop-2-ynyl)malonate) produced a cyclohexenone derivative (3-methyl-5-oxocyclohex-3-ene-1,1-dicarboxylate, 61%). Plausible reaction mechanisms are proposed for the formation of the products.
Department of Chemistry, Norwegian University of Science and Technology, NO-7491 Trondheim, Norway.
Christian
C
Sperger
Anne
A
Fiksdahl