Density Functional Study of Mo-Carbonyl-Catalyzed Alkynol Cycloisomerization: Comparison with W-Catalyzed Reaction

Mo-catalyzed endo-cycloisomerizations of alkynes tethered to alcohols have been studied using density functional theory, and comparisons were made with the W-catalyzed reaction. The cycloisomerization is initiated with the formation of metal alkyne pi complex and is followed by the rate-determining step, which transforms the pi complex to a vinylidene carbene complex, considered to be critical for endo-mode cyclization. Several different alkynols have been selected to investigate five- and six-membered ring endo-cycloisomerizations in the presence of Mo(CO)(5) catalyst. The energy barriers calculated for five- and six-membered ring cycloisomerizations are within a range of 25-30 kcal/mol for most cases studied, showing no significant energy difference between the two metals. The stabilization effect of THF and Et(3)N solvents and the substitution reaction of THF by alkynol substrates in the reaction process with Mo and W complexes are studied as well. The principal difference between Mo- and W-catalyzed cycloisomerization processes appears to be the initial formation of a pi complex, which is more stabilizing for formation of the W-alkyne vs Mo-alkyne complexes.