Theoretical investigation on the cycloaddition catalyzed by rhodium silylenoid to construct silicon-containing rings

Ma, Xiaoying; Liu, Siyuan; Liu, Tao

doi:10.1016/j.mcat.2022.112138

Cited by 2 publications

(1 citation statement)

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“…Thus, identifying the key factors that govern stereoselectivity is also interesting and informative. With theoretical investigation on the mechanism of NHC-catalyzed reactions at the core of the research activity in our group, − we now employ a theoretical investigation on the mechanism of NHC-catalyzed activation/transformation of 9 H -fluorene-1-carbaldehyde involving an o -QDM intermediate as key intermediate using the density functional theory (DFT) method, which has frequently used for mechanistic investigation of organocatalytic − and organometallic reactions. − …”

Section: Introductionmentioning

confidence: 99%

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

Luo,

Zhao,

Wang

2024

J. Phys. Chem. A

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N-heterocyclic carbene (NHC)-bound ortho-quinodimethane, served as a nucleophile, has occupied an important position for constructing various all-carbon or heterocyclic compounds and attracted increasing attention for the functionalization of benzylic carbon of aromatic aldehydes, whereas the mechanistic studies on the generation and transformations of dienolate intermediate are rare. In the present study, the mechanism of activation/transformation of aldehyde catalyzed by NHC was theoretically studied using the density functional theory (DFT) method. Based on the calculations, the nucleophilic addition process is the stereoselectivity-determining step with RSconfigured product being generated preferentially. Furthermore, non-covalent index (NCI) and atoms-in-molecules (AIM) analyses have been performed to disclose the origin of stereoselectivity, by which the larger number and stronger weak interactions are the key for stabilizing the low-energy transition state and thus leading to the stereoselectivity inducing.

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