Thiosemicarbazone organocatalysis: tetrahydropyranylation and 2-deoxygalactosylation reactions and kinetics-based mechanistic investigation

The first use of thiosemicarbazone-based organocatalysis was demonstrated on both tetrahydropyranylation and 2-deoxygalactosylation reactions. The organocatalysts were optimised using kinetics-based selection. The best catalyst outperformed previously reported thiourea catalysts for tetrahydropyrany...

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Autores principales: Larsen, Dennis, Langhorn, Line M., Akselsen, Olivia M., Nielsen, Bjarne E., Pittelkow, Michael
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5853554/
https://www.ncbi.nlm.nih.gov/pubmed/29568444
http://dx.doi.org/10.1039/c7sc03366d
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author Larsen, Dennis
Langhorn, Line M.
Akselsen, Olivia M.
Nielsen, Bjarne E.
Pittelkow, Michael
author_facet Larsen, Dennis
Langhorn, Line M.
Akselsen, Olivia M.
Nielsen, Bjarne E.
Pittelkow, Michael
author_sort Larsen, Dennis
collection PubMed
description The first use of thiosemicarbazone-based organocatalysis was demonstrated on both tetrahydropyranylation and 2-deoxygalactosylation reactions. The organocatalysts were optimised using kinetics-based selection. The best catalyst outperformed previously reported thiourea catalysts for tetrahydropyranylation by 50-fold. Hammett investigations of both the organocatalyst and the substrate indicate an oxyanion hole-like reaction mechanism.
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spelling pubmed-58535542018-03-22 Thiosemicarbazone organocatalysis: tetrahydropyranylation and 2-deoxygalactosylation reactions and kinetics-based mechanistic investigation Larsen, Dennis Langhorn, Line M. Akselsen, Olivia M. Nielsen, Bjarne E. Pittelkow, Michael Chem Sci Chemistry The first use of thiosemicarbazone-based organocatalysis was demonstrated on both tetrahydropyranylation and 2-deoxygalactosylation reactions. The organocatalysts were optimised using kinetics-based selection. The best catalyst outperformed previously reported thiourea catalysts for tetrahydropyranylation by 50-fold. Hammett investigations of both the organocatalyst and the substrate indicate an oxyanion hole-like reaction mechanism. Royal Society of Chemistry 2017-12-01 2017-10-06 /pmc/articles/PMC5853554/ /pubmed/29568444 http://dx.doi.org/10.1039/c7sc03366d Text en This journal is © The Royal Society of Chemistry 2017 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Larsen, Dennis
Langhorn, Line M.
Akselsen, Olivia M.
Nielsen, Bjarne E.
Pittelkow, Michael
Thiosemicarbazone organocatalysis: tetrahydropyranylation and 2-deoxygalactosylation reactions and kinetics-based mechanistic investigation
title Thiosemicarbazone organocatalysis: tetrahydropyranylation and 2-deoxygalactosylation reactions and kinetics-based mechanistic investigation
title_full Thiosemicarbazone organocatalysis: tetrahydropyranylation and 2-deoxygalactosylation reactions and kinetics-based mechanistic investigation
title_fullStr Thiosemicarbazone organocatalysis: tetrahydropyranylation and 2-deoxygalactosylation reactions and kinetics-based mechanistic investigation
title_full_unstemmed Thiosemicarbazone organocatalysis: tetrahydropyranylation and 2-deoxygalactosylation reactions and kinetics-based mechanistic investigation
title_short Thiosemicarbazone organocatalysis: tetrahydropyranylation and 2-deoxygalactosylation reactions and kinetics-based mechanistic investigation
title_sort thiosemicarbazone organocatalysis: tetrahydropyranylation and 2-deoxygalactosylation reactions and kinetics-based mechanistic investigation
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5853554/
https://www.ncbi.nlm.nih.gov/pubmed/29568444
http://dx.doi.org/10.1039/c7sc03366d
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AT akselsenoliviam thiosemicarbazoneorganocatalysistetrahydropyranylationand2deoxygalactosylationreactionsandkineticsbasedmechanisticinvestigation
AT nielsenbjarnee thiosemicarbazoneorganocatalysistetrahydropyranylationand2deoxygalactosylationreactionsandkineticsbasedmechanisticinvestigation
AT pittelkowmichael thiosemicarbazoneorganocatalysistetrahydropyranylationand2deoxygalactosylationreactionsandkineticsbasedmechanisticinvestigation

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