A silica-supported titanium catalyst for heterogeneous hydroamination and multicomponent coupling reactions

Abstract

Highly dehydrated silica gel, SiO₂⁷⁰⁰, gave a material with a total surface hydroxyl density of 0.31 ± 0.05 mmol g⁻¹, 0.9 ± 0.1 Si–OH sites per nm². Treatment of this material with Ti(NMe₂)₄ gave Ti(NMe₂)₃/SiO₂⁷⁰⁰, which is 1.50% ± 0.07 Ti, where the titanium is bound to the surface, on average, through a single O–Si–Ti linkage. This material was tested for its properties as a catalyst for C–N bond forming reactions and was found to be a competent alkyne hydroamination and iminoamination catalyst. For iminoamination, which is the 3-component coupling of an alkyne, primary amine, and isonitrile, this heterogeneous catalyst was able to carry out some catalyses faster than previously reported homogeneous catalysts with lower catalyst loadings. The material is also a catalyst for the addition of aniline to dicyclohexylcarbodiimide to form a substituted guanidine. In addition, a known quinoline with biological activity was prepared using the heterogeneous catalyst in a one-pot procedure using half the catalyst loading of the previously reported synthesis.