Kinetic and Structure–Activity Studies of the Triazolium Ion– catalyzed Intramolecular Stetter Reaction

Collett, Christopher J.; Young, Claire M.; Massey, Richard S.; O'Donoghue, AnnMarie C.; Smith, Andrew D

Abstract

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.

Citation

Collett, C. J., Young, C. M., Massey, R. S., O'Donoghue, A. C., & Smith, A. D. (2021). Kinetic and Structure–Activity Studies of the Triazolium Ion– catalyzed Intramolecular Stetter Reaction. European Journal of Organic Chemistry, 2021(26), 3670-3675. https://doi.org/10.1002/ejoc.202100384

• Journal Article Type: Article
• Online Publication Date: May 31, 2021
• Publication Date: Jul 15, 2021
• Deposit Date: May 7, 2021
• Publicly Available Date: Jul 6, 2021
• Journal: European Journal of Organic Chemistry
• Print ISSN: 1434-193X
• Electronic ISSN: 1099-0690
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 2021
• Issue: 26
• Pages: 3670-3675
• DOI: https://doi.org/10.1002/ejoc.202100384
• Public URL: https://durham-repository.worktribe.com/output/1248390
• Publisher URL: https://doi.org/10.1002/ejoc.202100384