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Characterization and Fate of a Septanosyl Ferrier Cation in the Gas and Solution Phases

[Image: see text] Ferrier reactions follow a mechanistic pathway whereby Lewis acid activation of a cyclic enol ether facilitates departure of an allylic leaving group to form a glycosyl Ferrier cation. Attack on the Ferrier cation provides a new acetal linkage concurrent with the transposition of t...

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Autores principales: Greis, Kim, Griesbach, Caleb E., Kirschbaum, Carla, Meijer, Gerard, von Helden, Gert, Pagel, Kevin, Peczuh, Mark W.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10167658/
https://www.ncbi.nlm.nih.gov/pubmed/37092271
http://dx.doi.org/10.1021/acs.joc.3c00079
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author Greis, Kim
Griesbach, Caleb E.
Kirschbaum, Carla
Meijer, Gerard
von Helden, Gert
Pagel, Kevin
Peczuh, Mark W.
author_facet Greis, Kim
Griesbach, Caleb E.
Kirschbaum, Carla
Meijer, Gerard
von Helden, Gert
Pagel, Kevin
Peczuh, Mark W.
author_sort Greis, Kim
collection PubMed
description [Image: see text] Ferrier reactions follow a mechanistic pathway whereby Lewis acid activation of a cyclic enol ether facilitates departure of an allylic leaving group to form a glycosyl Ferrier cation. Attack on the Ferrier cation provides a new acetal linkage concurrent with the transposition of the alkene moiety. The idiosyncratic outcomes of Ferrier reactions of seven-membered ring carbohydrate-based oxepines prompted an investigation of its corresponding septanosyl Ferrier cation. Experiments that characterized the ion, including gas-phase cryogenic IR spectroscopy matched with density functional theory-calculated spectra of candidate cation structures, as well as product analysis from solution-phase Ferrier reactions, are reported here. Results from both approaches revealed an inclination of the seven-membered ring cation to contract to five-membered ring structures. Gas-phase IR spectra matched best to calculated spectra of structures in which five-membered dioxolenium formation opened the oxepine ring. In the solution phase, an attack on the ion by water led to an acyclic enal that cyclized to a C-methylene-aldehydo arabinofuranoside species. Attack by allyl trimethylsilane, on the other hand, was diastereoselective and yielded a C-allyl septanoside.
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spelling pubmed-101676582023-05-10 Characterization and Fate of a Septanosyl Ferrier Cation in the Gas and Solution Phases Greis, Kim Griesbach, Caleb E. Kirschbaum, Carla Meijer, Gerard von Helden, Gert Pagel, Kevin Peczuh, Mark W. J Org Chem [Image: see text] Ferrier reactions follow a mechanistic pathway whereby Lewis acid activation of a cyclic enol ether facilitates departure of an allylic leaving group to form a glycosyl Ferrier cation. Attack on the Ferrier cation provides a new acetal linkage concurrent with the transposition of the alkene moiety. The idiosyncratic outcomes of Ferrier reactions of seven-membered ring carbohydrate-based oxepines prompted an investigation of its corresponding septanosyl Ferrier cation. Experiments that characterized the ion, including gas-phase cryogenic IR spectroscopy matched with density functional theory-calculated spectra of candidate cation structures, as well as product analysis from solution-phase Ferrier reactions, are reported here. Results from both approaches revealed an inclination of the seven-membered ring cation to contract to five-membered ring structures. Gas-phase IR spectra matched best to calculated spectra of structures in which five-membered dioxolenium formation opened the oxepine ring. In the solution phase, an attack on the ion by water led to an acyclic enal that cyclized to a C-methylene-aldehydo arabinofuranoside species. Attack by allyl trimethylsilane, on the other hand, was diastereoselective and yielded a C-allyl septanoside. American Chemical Society 2023-04-24 /pmc/articles/PMC10167658/ /pubmed/37092271 http://dx.doi.org/10.1021/acs.joc.3c00079 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Greis, Kim
Griesbach, Caleb E.
Kirschbaum, Carla
Meijer, Gerard
von Helden, Gert
Pagel, Kevin
Peczuh, Mark W.
Characterization and Fate of a Septanosyl Ferrier Cation in the Gas and Solution Phases
title Characterization and Fate of a Septanosyl Ferrier Cation in the Gas and Solution Phases
title_full Characterization and Fate of a Septanosyl Ferrier Cation in the Gas and Solution Phases
title_fullStr Characterization and Fate of a Septanosyl Ferrier Cation in the Gas and Solution Phases
title_full_unstemmed Characterization and Fate of a Septanosyl Ferrier Cation in the Gas and Solution Phases
title_short Characterization and Fate of a Septanosyl Ferrier Cation in the Gas and Solution Phases
title_sort characterization and fate of a septanosyl ferrier cation in the gas and solution phases
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10167658/
https://www.ncbi.nlm.nih.gov/pubmed/37092271
http://dx.doi.org/10.1021/acs.joc.3c00079
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