Experimental and Computational Studies of Anti‐Bredt Amidinium Salts |
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Authors: | Dr. David Martin Dr. Nicolas Lassauque Florian Steinmann Gerald Manuel Prof. Guy Bertrand |
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Affiliation: | UCSD‐CNRS Joint Research Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093 0343 (USA) |
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Abstract: | 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. |
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Keywords: | azomethineylides carbenes carbocations strained molecules substituent effects |
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