Kinetic and structure-activity studies of the triazolium Ion-catalyzed intramolecular stetter reaction

Christopher John Collett; Claire Mary Young; Richard. S. Massey; AnnMarie O'Donoghue; Andrew David Smith

doi:10.1002/ejoc.202100384

Kinetic and structure-activity studies of the triazolium Ion-catalyzed intramolecular stetter reaction

Christopher John Collett
, Claire Mary Young
, Richard. S. Massey
, AnnMarie O'Donoghue^*
, Andrew David Smith

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Article number	202100384
Pages (from-to)	3670-3675
Number of pages	7
Journal	European Journal of Organic Chemistry
Volume	2021
Issue number	26
Early online date	31 May 2021
DOIs	https://doi.org/10.1002/ejoc.202100384
Publication status	Published - 15 Jul 2021

Keywords

NHC
Breslow intermediate
Triazolium
Stetter reaction
Initial rates analysis

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10.1002/ejoc.202100384Licence: CC BY

Collett-2021-Kinetic-and-structure-EJOC-202100384-CCBY
Copyright © 2021 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 2.27 MBLicence: CC BY

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Underpinning Mechanistic Studies: Underpinning Mechanistic Studies of NHC-Organocatalysis: A Breslow Intermediate Reactivity Scale
Smith, A. (PI)
EPSRC
1/04/19 → 31/12/22
Project: Standard
N-Heterocyclic Carbenes as Asymmetric: N-Heterocyclic Carbenes as Asymmetric Organocatalysts: Reaction Development
Smith, A. (PI)
EPSRC
1/04/07 → 30/09/10
Project: Standard

Kinetic and Structure-Activity Studies of the Triazolium Ion- catalyzed Intramolecular Stetter Reaction (dataset)
Smith, A. D. (Creator) & Young, C. M. (Creator), University of St Andrews, 2 Jun 2021
DOI: 10.17630/7b18dcdd-72a3-4b26-909b-25ccd31cd58c
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@article{15ce3595a7b54b7a869296e6468dd2ad,

title = "Kinetic and structure-activity studies of the triazolium Ion-catalyzed intramolecular stetter reaction",

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.",

keywords = "NHC, Breslow intermediate, Triazolium, Stetter reaction, Initial rates analysis",

author = "Collett, \{Christopher John\} and Young, \{Claire Mary\} and Massey, \{Richard. S.\} and AnnMarie O'Donoghue and Smith, \{Andrew David\}",

note = "Funding: Engineering and Physical Sciences Research Council (Grant Number(s): EP/E03795X/1, EP/S019359/1).",

year = "2021",

month = jul,

day = "15",

doi = "10.1002/ejoc.202100384",

language = "English",

volume = "2021",

pages = "3670--3675",

journal = "European Journal of Organic Chemistry",

issn = "1434-193X",

publisher = "Wiley-VCH, Weinheim",

number = "26",

}

TY - JOUR

T1 - Kinetic and structure-activity studies of the triazolium Ion-catalyzed intramolecular stetter reaction

AU - Collett, Christopher John

AU - Young, Claire Mary

AU - Massey, Richard. S.

AU - O'Donoghue, AnnMarie

AU - Smith, Andrew David

N1 - Funding: Engineering and Physical Sciences Research Council (Grant Number(s): EP/E03795X/1, EP/S019359/1).

PY - 2021/7/15

Y1 - 2021/7/15

N2 - 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.

AB - 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.

KW - NHC

KW - Breslow intermediate

KW - Triazolium

KW - Stetter reaction

KW - Initial rates analysis

U2 - 10.1002/ejoc.202100384

DO - 10.1002/ejoc.202100384

M3 - Article

SN - 1434-193X

VL - 2021

SP - 3670

EP - 3675

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 26

M1 - 202100384

ER -

Kinetic and structure-activity studies of the triazolium Ion-catalyzed intramolecular stetter reaction

Abstract

Keywords

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Projects

Underpinning Mechanistic Studies: Underpinning Mechanistic Studies of NHC-Organocatalysis: A Breslow Intermediate Reactivity Scale

N-Heterocyclic Carbenes as Asymmetric: N-Heterocyclic Carbenes as Asymmetric Organocatalysts: Reaction Development

Datasets

Kinetic and Structure-Activity Studies of the Triazolium Ion- catalyzed Intramolecular Stetter Reaction (dataset)

Cite this