ArticleAngewandte Chemie (International ed. in English)2022
Formation of Breslow Intermediates from N-Heterocyclic Carbenes and Aldehydes Involves Autocatalysis by the Breslow Intermediate, and a Hemiacetal.
Article in Angewandte Chemie (International ed. in English), 2022. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 7 papers.
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Who cites it
7 citing papers in PubMed.
- Shedding Light on Synthetic Autocatalysis: From Conventional Closed-Shell Chemistries to Overlooked Open-Shell Occurrences.Chemistry (Weinheim an der Bergstrasse, Germany) · 2026Review
- Organocatalytic Thioesterification of a Conjugated α,β-Unsaturated Dialdehyde.International journal of molecular sciences · 2026Article
- Desymmetric esterification catalysed by bifunctional chiral N-heterocyclic carbenes provides access to inherently chiral calix[4]arenes.Nature communications · 2025Article
- Eco-Friendly Functionalization of Ynals with Thiols under Mild Conditions.International journal of molecular sciences · 2024Article
- Impact of Backbone Substitution on Organocatalytic Activity of Sterically Encumbered NHC in Benzoin Condensation.Molecules (Basel, Switzerland) · 2024Article
- Rate and equilibrium constants for the addition of triazolium salt derived N-heterocyclic carbenes to heteroaromatic aldehydes.Chemical science · 2022Article
- Formation of Breslow Intermediates from N-Heterocyclic Carbenes and Aldehydes Involves Autocatalysis by the Breslow Intermediate, and a Hemiacetal.Angewandte Chemie (International ed. in English) · 2022Article
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5 authors.
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Abstract
Under aprotic conditions, the stoichiometric reaction of N-heterocyclic carbenes (NHCs) such as imidazolidin-2-ylidenes with aldehydes affords Breslow Intermediates (BIs), involving a formal 1,2-C-to-O proton shift. We herein report kinetic studies (NMR), complemented by DFT calculations, on the mechanism of this kinetically disfavored H-translocation. Variable time normalization analysis (VTNA) revealed that the kinetic orders of the reactants vary for different NHC-to-aldehyde ratios, indicating different and ratio-dependent mechanistic regimes. We propose that for high NHC-to-aldehyde ratios, the H-shift takes place in the primary, zwitterionic NHC-aldehyde adduct. With excess aldehyde, the zwitterion is in equilibrium with a hemiacetal, in which the H-shift occurs. In both regimes, the critical H-shift is auto-catalyzed by the BI. Kinetic isotope effects observed for R-CDO are in line with our proposal. Furthermore, we detected an H-bonded complex of the BI with excess NHC (NMR).
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