Insights into the Nucleophilic Substitution of Pyridine at an Unsaturated Carbon Center

Overview

Journal RSC Adv

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 Apr 28

PMID 35479030

Authors

Pan Du

Jiyang Zhao

Shanshan Liu

Zhen Yue

Affiliations

Soon will be listed here.

Abstract

Bimolecular nucleophilic substitution (S2) is a fundamental reaction that has been widely studied. So far, the nucleophiles are mainly anionic species in S2 reactions. In this study, we use density functional theory calculations to assess the mechanisms of substitution of carbonyl, imidoyl, and vinyl compounds with a neutral nucleophile, pyridine. Charge decomposition analysis is performed to explore the main components of the transition state's LUMO. For reactions of imidoyl or carbonyl compounds with pyridine or Cl, the LUMOs of the transition states are composed of mixed orbitals originating from the nucleophile and the substrate. Considering the unique mixed nature of the orbitals, the reaction mode is termed S ( means mix). Moreover, the main components of the transition state's LUMO are pure σ* MO in the reactions of HC[double bond, length as m-dash]CHCl with pyridine or Cl. Computations were also performed for RY[double bond, length as m-dash]CHX substrates with different X and Y groups (X= Cl, Br, or F; Y = O, N, or C).

Citing Articles

Metal-Free Phosphination and Continued Functionalization of Pyridine: A Theoretical Study.

Du P, Yin Y, Shi D, Mao K, Yu Q, Zhao J Molecules. 2022; 27(17).

PMID: 36080460 PMC: 9457550. DOI: 10.3390/molecules27175694.

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