Readily available Ti-based in situ catalytic system for oxo/imido heterometathesis.

We investigate Ti(NEt2)4 supported on silica dehydroxylated at 700 °C as an easily accessible pre-catalyst for oxo/imido heterometathesis reactions. Being activated with TolNH2, the supported Ti amide (SiO)Ti(NEt2)3 (1) demonstrates catalytic activity in the imidation of ketones with N-sulfinylamines comparable with the most active previously described well-defined imido catalyst (SiO)Ti(NtBu)(Me2Pyr)(py)2 (2) (Me2Pyr = 2,5-dimethylpyrrolyl), which implies the in situ formation of surface imido species in this system. The materials obtained via treatment of 1 with anilines (TolNH2 (1a) and p-MeOC6H415NH2 (1b)) were studied with IR, EA and 1H, 13C, 15N and 2D solid-state NMR, although the proposed imido intermediate has not been detected, pointing towards tris-amides (SiO)Ti(NHC6H4X)3 (X = Me, OMe) being the major surface species in the isolated materials 1a and 1b. The system 1/TolNH2 was tested in a range of imidation reactions and demonstrated excellent performance for express high-yielding preparation of ketimines, formamidines, lactone imidates and sulfurdiimines, making it a convenient alternative to the well-defined supported Ti imido catalysts.