Gold-catalyzed intermolecular alkyne oxyarylation for C3-functionalization of benzothiophenes

Paige Rist; Richard Grainger; Paul Davies

doi:10.1021/acs.orglett.0c03596

Gold-catalyzed intermolecular alkyne oxyarylation for C3-functionalization of benzothiophenes

Chemistry

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Abstract

C3-selective C-C bond formation on benzothiophenes is challenging, and few direct functionalization methods are available. A gold-catalyzed reaction of alkynes with benzothiophene S-oxides provides regioselective entry into C3-alkylated benzothiophenes with the C7-alkylated isomer as the minor product. This oxyarylation reaction works with alkyl and aryl alkynes and substituted and unsubstituted benzothiophenes. Mechanistic studies identify that sulfoxide inhibits the catalyst [DTBPAu(PhCN)]SbF6, which also degrades and forms the unreactive complex [(DTBP)2Au]SbF6.

Original language	English
Pages (from-to)	642–646
Number of pages	5
Journal	Organic Letters
Volume	23
Issue number	3
Early online date	19 Jan 2021
DOIs	https://doi.org/10.1021/acs.orglett.0c03596
Publication status	Published - 5 Feb 2021

Bibliographical note

Funding Information:
We thank the EPSRC for a studentship to P.A.R. (EP/N509590/1). The authors gratefully acknowledge support from the Centre for Chemical and Materials Analysis in the School of Chemistry and Dr. Cécile le Duff for NMR support. P.W.D. is grateful to the Royal Society and the Leverhulme Trust for the award of a Senior Research Fellowship (SRF\R1\191033).

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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ristp2021goldcaFinal published version, 1.35 MBLicence: Creative Commons: Attribution (CC BY)

https://doi.org/10.1021/acs.orglett.0c03596Licence: Creative Commons: Attribution (CC BY)

1 Article

Regioselective functionalisation of dibenzothiophenes through gold-catalysed intermolecular alkyne oxyarylation
Davies, P., Grainger, R. & Barrett, M., 28 Aug 2015, In: Organic and Biomolecular Chemistry. 13, 32, p. 8676-8686 11 p.
Research output: Contribution to journal › Article › peer-review

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1 Finished

A mechanistic investigation into sulfur-enabled reactivity
Davies, P. (Principal Investigator)
The Royal Society
28/01/20 → 27/07/21
Project: Research Councils

Research data supporting the publication "Gold-Catalyzed Intermolecular Alkyne Oxyarylation for C3 Functionalization of Benzothiophenes"
Rist, P. (Creator), Grainger, R. (Supervisor) & Davies, P. (Supervisor), University of Birmingham, 14 Jan 2021
DOI: 10.25500/edata.bham.00000583
Dataset

Birmingham Environment for Academic Research (BEAR)
Facility/equipment: Equipment

Cite this

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abstract = "C3-selective C-C bond formation on benzothiophenes is challenging, and few direct functionalization methods are available. A gold-catalyzed reaction of alkynes with benzothiophene S-oxides provides regioselective entry into C3-alkylated benzothiophenes with the C7-alkylated isomer as the minor product. This oxyarylation reaction works with alkyl and aryl alkynes and substituted and unsubstituted benzothiophenes. Mechanistic studies identify that sulfoxide inhibits the catalyst [DTBPAu(PhCN)]SbF6, which also degrades and forms the unreactive complex [(DTBP)2Au]SbF6.",

author = "Paige Rist and Richard Grainger and Paul Davies",

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AB - C3-selective C-C bond formation on benzothiophenes is challenging, and few direct functionalization methods are available. A gold-catalyzed reaction of alkynes with benzothiophene S-oxides provides regioselective entry into C3-alkylated benzothiophenes with the C7-alkylated isomer as the minor product. This oxyarylation reaction works with alkyl and aryl alkynes and substituted and unsubstituted benzothiophenes. Mechanistic studies identify that sulfoxide inhibits the catalyst [DTBPAu(PhCN)]SbF6, which also degrades and forms the unreactive complex [(DTBP)2Au]SbF6.

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Gold-catalyzed intermolecular alkyne oxyarylation for C3-functionalization of benzothiophenes

Abstract

Bibliographical note

ASJC Scopus subject areas

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Research output

Regioselective functionalisation of dibenzothiophenes through gold-catalysed intermolecular alkyne oxyarylation

Projects

A mechanistic investigation into sulfur-enabled reactivity

Datasets

Research data supporting the publication "Gold-Catalyzed Intermolecular Alkyne Oxyarylation for C3 Functionalization of Benzothiophenes"

Equipment

Birmingham Environment for Academic Research (BEAR)

Cite this