Tungsten Oxide Dispersed on Silica as Robust and Readily Available Oxo/Imido Heterometathesis Catalyst.

Continuing our investigation of catalytic oxo/imido heterometathesis as novel water-free method for C=N bond construction, we report here the application of classical transition metal oxides dispersed on silica (MOx/SiO2, M=V, Mo, W) as cheap, robust and readily available alternative to the catalysts prepared via Surface Organometallic Chemistry (SOMC). The oxide materials demonstrated activity in heterometathetical imidation of ketones, WO3/SiO2 being the most efficient. We also describe a new well-defined supported W imido complex (≡SiO)W(=NMes)2(Me2Pyr) (Mes=2,4,6-Me3C6H2, Me2Pyr=2,5-dimethylpyrrolyl) and characterize it with SOMC protocols, which allowed us to identify the position of W on the oxo/imido heterometathesis activity scale (Mo<W<Ta) and showed that W in fact provides an optimal balance between activity and stability. Noteworthy, the performance of WO3/SiO2 was only slightly inferior to that of the SOMC analog enabling the efficient synthesis of a broad range of ketimines hardly accessible by classical methods, in most cases W being a competitive and robust alternative to the most active albeit highly sensitive Ti imido systems. Combined with the availability of the catalyst, this facilitates a more widespread application of heterometathesis methodology in organic synthesis including potential larger scale applications.