Carbenes and Nitrenes
Résumé
A general review has appeared on catalyst design assisted by computations featuring some examples of carbenes acting either as organocatalysts or in situ generated reagents in metal-catalysed reactions. The decomposition of propylamine and propylammonium in the gas phase has been investigated by density functional theory and composite quantum chemistry methods. The formation of carbene–borane complexes has found numerous applications in recent years and allowed the identification of unprecedented reaction mechanisms. Computational studies have been conducted on the reaction mechanism of lithium and magnesium carbenoid cyclopropanations. The reactivity of photogenerated diphenylcarbene has been found to be controlled by the presence of additional protic molecules. Under metal-free conditions, nitrene-transfer reactions to olefins are still challenging. The development and optimization of aziridination reactions under transition metal catalysis are still attracting much attention.
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