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Metal Triflate-Promoted Allylic Substitution Reactions of Cinnamyl Alcohol in the Presence of Orthoesters and Acetals

[Image: see text] 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...

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Autores principales: Chaffey, Dawn R., Alamillo-Ferrer, Carla, Davies, Thomas E., Taylor, Stuart H., Tomkinson, Nicholas C. O., Graham, Andrew E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6776978/
https://www.ncbi.nlm.nih.gov/pubmed/31592469
http://dx.doi.org/10.1021/acsomega.9b02059
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author Chaffey, Dawn R.
Alamillo-Ferrer, Carla
Davies, Thomas E.
Taylor, Stuart H.
Tomkinson, Nicholas C. O.
Graham, Andrew E.
author_facet Chaffey, Dawn R.
Alamillo-Ferrer, Carla
Davies, Thomas E.
Taylor, Stuart H.
Tomkinson, Nicholas C. O.
Graham, Andrew E.
author_sort Chaffey, Dawn R.
collection PubMed
description [Image: see text] 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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spelling pubmed-67769782019-10-07 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. ACS Omega [Image: see text] 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. American Chemical Society 2019-09-23 /pmc/articles/PMC6776978/ /pubmed/31592469 http://dx.doi.org/10.1021/acsomega.9b02059 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle 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
title Metal Triflate-Promoted Allylic Substitution Reactions of Cinnamyl Alcohol in the Presence of Orthoesters and Acetals
title_full Metal Triflate-Promoted Allylic Substitution Reactions of Cinnamyl Alcohol in the Presence of Orthoesters and Acetals
title_fullStr Metal Triflate-Promoted Allylic Substitution Reactions of Cinnamyl Alcohol in the Presence of Orthoesters and Acetals
title_full_unstemmed Metal Triflate-Promoted Allylic Substitution Reactions of Cinnamyl Alcohol in the Presence of Orthoesters and Acetals
title_short Metal Triflate-Promoted Allylic Substitution Reactions of Cinnamyl Alcohol in the Presence of Orthoesters and Acetals
title_sort metal triflate-promoted allylic substitution reactions of cinnamyl alcohol in the presence of orthoesters and acetals
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6776978/
https://www.ncbi.nlm.nih.gov/pubmed/31592469
http://dx.doi.org/10.1021/acsomega.9b02059
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