The Steglich Rearrangement of 2-Oxindole Derivatives Promoted by Anion-based Nucleophilic Catalysis

Cristina Trujillo; Mili Litvajova; Sarah A. Cronin; Ryan Craig; Stephen J. Connon

doi:10.1002/cctc.201900756

The Steglich Rearrangement of 2-Oxindole Derivatives Promoted by Anion-based Nucleophilic Catalysis

Cristina Trujillo^*, Mili Litvajova, Sarah A. Cronin, Ryan Craig, Stephen J. Connon

^*Corresponding author for this work

Computational and Theoretical Chemistry

University of Dublin Trinity College

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

Abstract

The first small anion-triggered Steglich rearrangements are reported. Tetrabutylammonium carboxylates-, cyanide- and fluoride promote the O- to C-acyl transfer of a range of O-acylated oxindoles to form 3,3-disubstituted oxindole products with new quaternary stereocentres. DFT calculations on the TBAF-mediated reaction strongly support a nucleophilic catalysis mechanism involving initial attack of fluoride on the O-acyl group to give an enolate and an acyl fluoride in the rate determining step.

Original language	English
Pages (from-to)	3776-3780
Number of pages	5
Journal	ChemCatChem
Volume	11
Issue number	16
Early online date	31 May 2019
DOIs	https://doi.org/10.1002/cctc.201900756
Publication status	Published - 21 Aug 2019

Keywords

catalysis
DFT
fluoride
oxindoles
Steglich rearrangement

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title = "The Steglich Rearrangement of 2-Oxindole Derivatives Promoted by Anion-based Nucleophilic Catalysis",

abstract = "The first small anion-triggered Steglich rearrangements are reported. Tetrabutylammonium carboxylates-, cyanide- and fluoride promote the O- to C-acyl transfer of a range of O-acylated oxindoles to form 3,3-disubstituted oxindole products with new quaternary stereocentres. DFT calculations on the TBAF-mediated reaction strongly support a nucleophilic catalysis mechanism involving initial attack of fluoride on the O-acyl group to give an enolate and an acyl fluoride in the rate determining step.",

keywords = "catalysis, DFT, fluoride, oxindoles, Steglich rearrangement",

author = "Cristina Trujillo and Mili Litvajova and Cronin, {Sarah A.} and Ryan Craig and Connon, {Stephen J.}",

note = "Funding Information: This publication has emanated from research supported by the Science Foundation Ireland (SFI-12-IA-1645) and (SFI 18/SIRG/5517). We are grateful to the Irish Centre for High-End Computing (ICHEC) for the provision of computational facilities. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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doi = "10.1002/cctc.201900756",

language = "English",

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AU - Trujillo, Cristina

AU - Litvajova, Mili

AU - Cronin, Sarah A.

AU - Craig, Ryan

AU - Connon, Stephen J.

N1 - Funding Information: This publication has emanated from research supported by the Science Foundation Ireland (SFI-12-IA-1645) and (SFI 18/SIRG/5517). We are grateful to the Irish Centre for High-End Computing (ICHEC) for the provision of computational facilities. Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/8/21

Y1 - 2019/8/21

N2 - The first small anion-triggered Steglich rearrangements are reported. Tetrabutylammonium carboxylates-, cyanide- and fluoride promote the O- to C-acyl transfer of a range of O-acylated oxindoles to form 3,3-disubstituted oxindole products with new quaternary stereocentres. DFT calculations on the TBAF-mediated reaction strongly support a nucleophilic catalysis mechanism involving initial attack of fluoride on the O-acyl group to give an enolate and an acyl fluoride in the rate determining step.

AB - The first small anion-triggered Steglich rearrangements are reported. Tetrabutylammonium carboxylates-, cyanide- and fluoride promote the O- to C-acyl transfer of a range of O-acylated oxindoles to form 3,3-disubstituted oxindole products with new quaternary stereocentres. DFT calculations on the TBAF-mediated reaction strongly support a nucleophilic catalysis mechanism involving initial attack of fluoride on the O-acyl group to give an enolate and an acyl fluoride in the rate determining step.

KW - catalysis

KW - DFT

KW - fluoride

KW - oxindoles

KW - Steglich rearrangement

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DO - 10.1002/cctc.201900756

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The Steglich Rearrangement of 2-Oxindole Derivatives Promoted by Anion-based Nucleophilic Catalysis

Abstract

Keywords

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