Kinetic and Structure‐Activity Studies of the Triazolium Ion‐ Catalyzed Intramolecular Stetter Reaction. Issue 26 (31st May 2021)

• Record Type: Journal Article
• Authors: Collett, Christopher J.; Young, Claire M.; Massey, Richard S.; O'Donoghue, AnnMarie C.; Smith, Andrew D.
• Is Part Of: European journal of organic chemistry. Issue 26(2021)
• Page Start: 3670
• Page End: 3675
• Publication Date: 2021-05-31
• Subjects: Breslow intermediate -- Initial rates analysis -- NHC -- Stetter reaction -- Triazolium; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.202100384
• Languages: English
• ISSNs: 1434-193X

Abstract

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. 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. The reported data are consistent with deprotonation to form the Breslow intermediate being turnover‐limiting in this process.