1394231-76-5Relevant academic research and scientific papers
Experimental and computational studies of anti-bredt amidinium salts
Martin, David,Lassauque, Nicolas,Steinmann, Florian,Manuel, Gerald,Bertrand, Guy
, p. 14895 - 14901 (2013/11/06)
Experimental and computational investigations of anti-Bredt amidinium salts are presented. Calculations show that the pyramidalization of an amino group can significantly destabilize the formal carbocation center of amidiniums, due to the decreased π donation. In some cases, the unfavorable -I effect of nitrogen surpasses its beneficial +M effect, and amidiniums become less stable than iminiums. It is shown that although 1-aza-3-azonia[3.3.1]bicyclo-non-2-enes can be isolated, they feature a nonclassical reactivity, which is more typical for iminium than amidinium salts, such as pronounced electrophilicity and azomethineylide instead of carbene formation. Copyright
A cyclic diaminocarbene with a pyramidalized nitrogen atom: A stable N-heterocyclic carbene with enhanced electrophilicity
Martin, David,Lassauque, Nicolas,Donnadieu, Bruno,Bertrand, Guy
experimental part, p. 6172 - 6175 (2012/08/14)
An anti-Bredt NHC! Placing one of the adjacent nitrogen atoms of an NHC in the bridgehead position of a bicyclic scaffold prevents the donation of its lone pair. Thus, the π-electron-accepting properties of the carbene center are enhanced, while the strong -electron-donating properties of classical NHCs are retained. Copyright
