Metal triflate-promoted allylic substitution reactions of cinnamyl alcohol in the presence of orthoesters and acetals

Dawn R. Chaffey, Carla Alamillo-Ferrer, Thomas E. Davies, Stuart H. Taylor, Nicholas C. O. Tomkinson, Andrew E. Graham

Research output: Contribution to journalArticle

Abstract

The product distribution of ethers formed from the reaction of cinnamyl alcohol with orthoesters in the presence of indium (III) triflate (InOTf)3 is dependent on both the reaction temperature and catalyst loading. Carrying out the reaction at room temperature under low loadings of the catalyst leads to a facile reaction generating the unexpected secondary allyl ether as the major product. In contrast, carrying out the reaction under higher catalyst loadings at elevated temperatures provides the expected primary linear ether in high yield and with excellent selectivity. The etherification reaction is also effective in the presence of acetals and ketals in place of orthoesters and allows for the development of the procedure to encompass a telescoped etherification protocol in which the acetal is generated in situ.

Original languageEnglish
Pages (from-to)15985-15991
Number of pages7
JournalACS Omega
Volume4
Issue number14
Early online date23 Sep 2019
DOIs
Publication statusPublished - 1 Oct 2019

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Acetals
Ethers
Alcohols
Substitution reactions
Metals
Ether
Catalysts
Indium
Temperature
cinnamyl alcohol

Keywords

  • cinnamyl alcohol
  • orthoesters
  • etherification

Cite this

Chaffey, Dawn R. ; Alamillo-Ferrer, Carla ; Davies, Thomas E. ; Taylor, Stuart H. ; Tomkinson, Nicholas C. O. ; Graham, Andrew E. / Metal triflate-promoted allylic substitution reactions of cinnamyl alcohol in the presence of orthoesters and acetals. In: ACS Omega. 2019 ; Vol. 4, No. 14. pp. 15985-15991.
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Metal triflate-promoted allylic substitution reactions of cinnamyl alcohol in the presence of orthoesters and acetals. / Chaffey, Dawn R.; Alamillo-Ferrer, Carla; Davies, Thomas E.; Taylor, Stuart H.; Tomkinson, Nicholas C. O.; Graham, Andrew E.

In: ACS Omega, Vol. 4, No. 14, 01.10.2019, p. 15985-15991.

Research output: Contribution to journalArticle

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T1 - Metal triflate-promoted allylic substitution reactions of cinnamyl alcohol in the presence of orthoesters and acetals

AU - Chaffey, Dawn R.

AU - Alamillo-Ferrer, Carla

AU - Davies, Thomas E.

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AU - Tomkinson, Nicholas C. O.

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AB - The product distribution of ethers formed from the reaction of cinnamyl alcohol with orthoesters in the presence of indium (III) triflate (InOTf)3 is dependent on both the reaction temperature and catalyst loading. Carrying out the reaction at room temperature under low loadings of the catalyst leads to a facile reaction generating the unexpected secondary allyl ether as the major product. In contrast, carrying out the reaction under higher catalyst loadings at elevated temperatures provides the expected primary linear ether in high yield and with excellent selectivity. The etherification reaction is also effective in the presence of acetals and ketals in place of orthoesters and allows for the development of the procedure to encompass a telescoped etherification protocol in which the acetal is generated in situ.

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