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Oxo-Rhenium-Mediated Allylation of Furanoside Derivatives: A Computational Study on the Mechanism and the Stereoselectivity

[Image: see text] Properly substituted tetrahydrofuran (THF) rings are important building blocks in the synthesis of many natural metabolites. Having reliable procedures to control the stereoselectivity at the THF core while decorating it with different substituents is a fundamental requirement to a...

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Autores principales: Casali, Emanuele, Porta, Alessio, Toma, Lucio, Zanoni, Giuseppe
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9361356/
https://www.ncbi.nlm.nih.gov/pubmed/35820228
http://dx.doi.org/10.1021/acs.joc.2c00393
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author Casali, Emanuele
Porta, Alessio
Toma, Lucio
Zanoni, Giuseppe
author_facet Casali, Emanuele
Porta, Alessio
Toma, Lucio
Zanoni, Giuseppe
author_sort Casali, Emanuele
collection PubMed
description [Image: see text] Properly substituted tetrahydrofuran (THF) rings are important building blocks in the synthesis of many natural metabolites. Having reliable procedures to control the stereoselectivity at the THF core while decorating it with different substituents is a fundamental requirement to achieve and fulfill the complexity of nature. We recently reported a new chemical approach to control the stereochemistry in the alkylation and arylation of furanoside derivatives by using a rhenium(V) complex to form an intermediate oxo-carbenium species able to react with proper soft nucleophiles. Here, we describe theoretical calculations, performed at the DFT B3LYP level, to disclose the important mechanistic features which regulate the entire catalytic cycle of the reaction of mono- and disubstituted furanosides with allyltrimethylsilane catalyzed by Re(O)Cl(3)(OPPh(3))(Me(2)S). Moreover, the key factors governing the allylation step were investigated, confirming that the stereoselectivity, which is independent of the anomeric configuration of starting acetal, mainly arises from the orientation of the substituent at C-4, with only marginal contribution of the substituent at C-5. Finally, puckering Cremer–Pople parameters were used to take trace of the structural modifications throughout the catalytic cycle.
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spelling pubmed-93613562022-08-10 Oxo-Rhenium-Mediated Allylation of Furanoside Derivatives: A Computational Study on the Mechanism and the Stereoselectivity Casali, Emanuele Porta, Alessio Toma, Lucio Zanoni, Giuseppe J Org Chem [Image: see text] Properly substituted tetrahydrofuran (THF) rings are important building blocks in the synthesis of many natural metabolites. Having reliable procedures to control the stereoselectivity at the THF core while decorating it with different substituents is a fundamental requirement to achieve and fulfill the complexity of nature. We recently reported a new chemical approach to control the stereochemistry in the alkylation and arylation of furanoside derivatives by using a rhenium(V) complex to form an intermediate oxo-carbenium species able to react with proper soft nucleophiles. Here, we describe theoretical calculations, performed at the DFT B3LYP level, to disclose the important mechanistic features which regulate the entire catalytic cycle of the reaction of mono- and disubstituted furanosides with allyltrimethylsilane catalyzed by Re(O)Cl(3)(OPPh(3))(Me(2)S). Moreover, the key factors governing the allylation step were investigated, confirming that the stereoselectivity, which is independent of the anomeric configuration of starting acetal, mainly arises from the orientation of the substituent at C-4, with only marginal contribution of the substituent at C-5. Finally, puckering Cremer–Pople parameters were used to take trace of the structural modifications throughout the catalytic cycle. American Chemical Society 2022-07-12 2022-08-05 /pmc/articles/PMC9361356/ /pubmed/35820228 http://dx.doi.org/10.1021/acs.joc.2c00393 Text en © 2022 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 Casali, Emanuele
Porta, Alessio
Toma, Lucio
Zanoni, Giuseppe
Oxo-Rhenium-Mediated Allylation of Furanoside Derivatives: A Computational Study on the Mechanism and the Stereoselectivity
title Oxo-Rhenium-Mediated Allylation of Furanoside Derivatives: A Computational Study on the Mechanism and the Stereoselectivity
title_full Oxo-Rhenium-Mediated Allylation of Furanoside Derivatives: A Computational Study on the Mechanism and the Stereoselectivity
title_fullStr Oxo-Rhenium-Mediated Allylation of Furanoside Derivatives: A Computational Study on the Mechanism and the Stereoselectivity
title_full_unstemmed Oxo-Rhenium-Mediated Allylation of Furanoside Derivatives: A Computational Study on the Mechanism and the Stereoselectivity
title_short Oxo-Rhenium-Mediated Allylation of Furanoside Derivatives: A Computational Study on the Mechanism and the Stereoselectivity
title_sort oxo-rhenium-mediated allylation of furanoside derivatives: a computational study on the mechanism and the stereoselectivity
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9361356/
https://www.ncbi.nlm.nih.gov/pubmed/35820228
http://dx.doi.org/10.1021/acs.joc.2c00393
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