Exploring a general mechanistic map on NHC-catalyzed activation/transformation reactions of saturated carboxylic anhydrides

Abstract

A general mechanistic map involving multiple intermediates and pathways has been proposed and systmatically studied for NHC-catalyzed transformation reactions of saturated carboxylic anhydrides. Based on the map, the origin of...

Disclosing the mechanism and origin of stereoselectivity of the NHC-catalyzed transformation reaction of enals with acyl azolium as a key intermediate

“…The energy barrier of this pathway is only 14.6 kcal mol −1 , which is much lower than those of the other two pathways and is consistent with the previous theoretical studies. 20,21…”

Mechanism and Origin of Stereoselectivity of N-Heterocyclic Carbene (NHC)-Catalyzed Transformation Reaction of Benzaldehyde with o-QDM as Key Intermediate: A DFT Study

“…(The detailed derivation of calculated ee value is provided in Part 9 of the Supporting Information.) Then, we turn to disclose the key factors that induce the formation of RS -configured product as a major isomer. The widely used atoms-in-molecules (AIM) and non-covalent index (NCI) analyses, which have been successfully utilized to recognize the predominant weak interactions, are then performed to distinguish the types and strengths of the weak interactions in the stereoselective transition states. − …”

N-Heterocyclic carbene catalyzed synthesis of benzotrifluorides from enals and β-trifluoromethylenones

“…The lactonization of adduct III affords the bicyclic adduct IV and liberates the NHC catalyst. The decarboxylation of adduct IV possibly accelerated by a Brønsted acid (DBU·H + ) 20 and the following oxidative aromatization with DQ give the final multi-substituted benzotrifluoride 3 .…”