New generation of nitrenium salts: catalytic hydrosilylation of imines and a mechanism of action of nitrogen Lewis acids

29 March 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Nitrogen Lewis acids (NLAs) are emerging as a powerful tool in strong bond activation and catalysis. Till now, N,N-dialkyl-nitrenium salts were known and utilized in chemical transformations. In this article, we report on the synthesis and characterization of a new generation of nitrenium-based Lewis acids – N,N-diaryl-substituted naphthotriazinium salts, which open a door to libraries of stereoelectronically modifiable catalysts. We exemplify the potency of these new Lewis acidic catalysts in a gram-scale hydrosilylation of various ketimines and aldimines in yields up to 99% and a catalyst loading as low as 0.1mol%. Notably, dialkyl-nitrenium salts proved inefficient in this reaction. Based on our experimental and theoretical studies, we elucidated, for the first time, the mechanistic action of nitrenium Lewis acids in such reduction-type reactions, demonstrating a unique hydridic behavior of N-H bonds in triazanes.


Lewis acids

Supplementary materials

Supporting Information
Full experimental details, synthetic procedures, characterization data, copies of NMR spectra, crystallographic data, and computational methods and data.


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