Homogeneous Catalytic Formation of Carbon-Nitrogen Bonds. 2. Catalytic Activation of the Silicon-Nitrogen Bond

Article abstract of DOI:10.1021/jo00163a023

The catalytic formation of new carbon-nitrogen single bonds can be promoted via catalytic activation of silicon-nitrogen bonds.Silazanes, compounds containing Si-N bonds, will react, in the presence of a catalyst, with compounds containing carbon-oxygen double bonds to form new C-N and Si-O bonds concurrently.Thus, CO2 and phenyl isocyanate can be reacted with a number of silazane compounds to give urethane and urea derivatives in 60-90percent yields.In the absence of catalysts, the identical reactions either do not proceed or go to less than 20percent conversion.Aldehydes and ketones also react in a similar manner to give imines and enamines, respectively.A variety of group 8 metals have been found to activate the Si-N bond in the catalytic formation of PhCH=NPh from PhNHSiM3 and PhCHO.Iron and rhodium catalysts were found to be the most active for this reaction.The catalytic activation of Si-N bonds was also found useful in the ring-opening oligomerization of in the presence of (Me3Si)2NH.