Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes
Due to the synthetic advantages presented by the dual-gold-catalysed hydrophenoxylation of alkynes, a thorough study of this reaction was carried out in order to fully define the scope and limitations of the methodology. The protocol tolerates a wide range of functional groups, such as nitriles, ket...
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doaj-c8e60b79cdc149d496edae2f84c93ae22021-02-02T03:25:46ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972016-02-0112117217810.3762/bjoc.12.191860-5397-12-19Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynesAdrián Gómez-Suárez0Yoshihiro Oonishi1Anthony R. Martin2Steven P. Nolan3EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST, U.KEaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST, U.KEaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST, U.KChemistry Department, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi ArabiaDue to the synthetic advantages presented by the dual-gold-catalysed hydrophenoxylation of alkynes, a thorough study of this reaction was carried out in order to fully define the scope and limitations of the methodology. The protocol tolerates a wide range of functional groups, such as nitriles, ketones, esters, aldehydes, ketals, naphthyls, allyls or polyphenols, in a milder and more efficient manner than the previously reported methodologies. We have also identified that while we are able to use highly steric hindered phenols, small changes on the steric bulk of the alkynes have a dramatic effect on the reactivity. More importantly, we have observed that the use of substrates that facilitate the formation of diaurated species such as gem-diaurated or σ,π-digold–acetylide species, hinder the catalytic activity. Moreover, we have identified that the use of directing groups in unsymmetrical alkynes can help to achieve high regioselectivity in the hydrophenoxylation.https://doi.org/10.3762/bjoc.12.19cooperative catalysisgold catalysishydrophenoxylationN-heterocyclic carbenevinyl ethers |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Adrián Gómez-Suárez Yoshihiro Oonishi Anthony R. Martin Steven P. Nolan |
spellingShingle |
Adrián Gómez-Suárez Yoshihiro Oonishi Anthony R. Martin Steven P. Nolan Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes Beilstein Journal of Organic Chemistry cooperative catalysis gold catalysis hydrophenoxylation N-heterocyclic carbene vinyl ethers |
author_facet |
Adrián Gómez-Suárez Yoshihiro Oonishi Anthony R. Martin Steven P. Nolan |
author_sort |
Adrián Gómez-Suárez |
title |
Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes |
title_short |
Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes |
title_full |
Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes |
title_fullStr |
Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes |
title_full_unstemmed |
Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes |
title_sort |
scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes |
publisher |
Beilstein-Institut |
series |
Beilstein Journal of Organic Chemistry |
issn |
1860-5397 |
publishDate |
2016-02-01 |
description |
Due to the synthetic advantages presented by the dual-gold-catalysed hydrophenoxylation of alkynes, a thorough study of this reaction was carried out in order to fully define the scope and limitations of the methodology. The protocol tolerates a wide range of functional groups, such as nitriles, ketones, esters, aldehydes, ketals, naphthyls, allyls or polyphenols, in a milder and more efficient manner than the previously reported methodologies. We have also identified that while we are able to use highly steric hindered phenols, small changes on the steric bulk of the alkynes have a dramatic effect on the reactivity. More importantly, we have observed that the use of substrates that facilitate the formation of diaurated species such as gem-diaurated or σ,π-digold–acetylide species, hinder the catalytic activity. Moreover, we have identified that the use of directing groups in unsymmetrical alkynes can help to achieve high regioselectivity in the hydrophenoxylation. |
topic |
cooperative catalysis gold catalysis hydrophenoxylation N-heterocyclic carbene vinyl ethers |
url |
https://doi.org/10.3762/bjoc.12.19 |
work_keys_str_mv |
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