Impact of Backbone Substitution on Organocatalytic Activity of Sterically Encumbered NHC in Benzoin Condensation-Reference-Cited by-同舟云学术

Impact of Backbone Substitution on Organocatalytic Activity of Sterically Encumbered NHC in Benzoin Condensation

Published:2024-04-10 Issue:8 Volume:29 Page:1704
ISSN:1420-3049
Container-title:Molecules
language:en
Short-container-title:Molecules

Author:

Aysin Rinat R.¹^ORCID,Galkin Konstantin I.²³^ORCID

Affiliation:

1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Street 28, bld. 1, 119991 Moscow, Russia

2. N. D. Zelinsky Institute of Organic Chemistry, Leninsky Prospect 47, Russian Academy of Sciences, 119991 Moscow, Russia

3. Laboratory of Green Chemistry, Bauman Moscow State Technical University, 2nd Baumanskaya Street 5/1, 105005 Moscow, Russia

Abstract

In this study, we provide a theoretical explanation for the experimentally observed decrease in the organocatalytic activity of N-aryl imidazolylidenes methylated at the C4/5-H positions in the benzoin condensation of aromatic aldehydes. A comparative quantum chemical study of energy profiles for the NHC-mediated benzoin condensation of furfural has revealed a high energy barrier to the formation of the IPrMe-based furanic Breslow intermediate that can be attributed to the negative steric interactions between the imidazole backbone methyl groups and N-aryl substituents.

Funder

Russian Science Foundation

Ministry of Science and Higher Education of the Russian Federation

Publisher

MDPI AG

Link

https://www.mdpi.com/1420-3049/29/8/1704/pdf

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