Kinetic and Structure‐Activity Studies of the Triazolium Ion‐ Catalyzed Intramolecular Stetter Reaction

Mechanistic studies of the triazolium ion‐catalyzed intramolecular Stetter reaction using initial rates analysis in NEt3/NEt3 ⋅ HCl buffered methanol showed the reaction to be first‐order in catalyst and zero‐order in aldehyde over a broad range of aldehyde concentrations. The observed reaction rate...

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Bibliographic Details
Published in:European journal of organic chemistry 2021-07, Vol.2021 (26), p.3670-3675
Main Authors: Collett, Christopher J., Young, Claire M., Massey, Richard S., O'Donoghue, AnnMarie C., Smith, Andrew D.
Format: Article
Language:English
Subjects:
Aldehydes
Breslow intermediate
Catalysts
Initial rates analysis
Isomerization
NHC
Stetter reaction
Substrates
Triazolium
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Summary:Mechanistic studies of the triazolium ion‐catalyzed intramolecular Stetter reaction using initial rates analysis in NEt3/NEt3 ⋅ HCl buffered methanol showed the reaction to be first‐order in catalyst and zero‐order in aldehyde over a broad range of aldehyde concentrations. The observed reaction rate is higher for catalysts bearing N‐aryl substituents with electron‐withdrawing groups. A concurrent, NHC‐independent substrate isomerization was also observed and found to demonstrate a first‐order dependence on aldehyde concentration. The reported data are consistent with deprotonation to form the Breslow intermediate being turnover‐limiting in this process. Mechanistic studies of the triazolium ion‐catalyzed intramolecular Stetter reaction using initial rates analysis in NEt3/NEt3 ⋅ HCl buffered methanol showed the reaction to be first order in catalyst and zero order in aldehyde. The reported data are consistent with deprotonation to form the Breslow intermediate being turnover‐limiting in this process.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.202100384