Highly Regioselective [2 + 2 + 2] Cycloaddition of Terminal Alkynes Catalyzed by η6-Arene Complexes of Titanium Supported by Dimethylsilyl-Bridged p-tert-Butyl Calix[4]arene Ligand Academic Article uri icon

abstract

  • Two new Ti-η6-arene complexes [(DMSC)Ti{η6-1,2,4- C6H3(SiMe3)3}] (6) and [(DMSC)Ti{η6-1,3,5-C6H3Bu(t)3}] (7) containing 1,2-alternate, Me2Si-bridged p-tert-butylcalix[4]arene (DMSC) ancillary ligand have been synthesized. The solid-state structure of 6 revealed a highly folded arene ligand [with a dihedral angle of 29.7(7)°] and suggests that 6 is better described as a 7-titananorbornadiene species. Both 6 and 7 are efficient catalysts for highly regioselective [2 + 2 + 2] cycloaddition of terminal alkynes to yield 1,2,4-substituted benzenes. Kinetic studies of the catalytic [2 + 2 + 2] cycloaddition of Me3SiC≡CH revealed first-order dependence on [6] and [Me3SiC≡CH]; and activation parameters, ΔH(+) = 14 kcal/mol, and ΔS(+) = -11 cal/mol K, that are consistent with an associative mechanism. The reaction rate is influenced by the steric requirements of both the alkyne and the η6-arene compound. The high selectivity for 1,2,4-substituted benzene may be understood in terms of the directing influence of the DMSC ligand.

author list (cited authors)

  • Ozerov, O. V., Patrick, B. O., & Ladipo, F. T

complete list of authors

  • Ozerov, Oleg V||Patrick, Brian O||Ladipo, Folami T

publication date

  • January 1, 2000 11:11 AM