Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp(3) C–O Bonds in Cyclic Acetals

[Image: see text] A dual catalytic manifold that enables site-selective functionalization of unactivated sp(3) C–O bonds in cyclic acetals with aryl and alkyl halides is reported. The reaction is triggered by an appropriate σ*–p orbital overlap prior to sp(3) C–O cleavage, thus highlighting the impo...

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Autores principales: Romano, Ciro, Talavera, Laura, Gómez-Bengoa, Enrique, Martin, Ruben
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9264358/
https://www.ncbi.nlm.nih.gov/pubmed/35749319
http://dx.doi.org/10.1021/jacs.2c04513
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author Romano, Ciro
Talavera, Laura
Gómez-Bengoa, Enrique
Martin, Ruben
author_facet Romano, Ciro
Talavera, Laura
Gómez-Bengoa, Enrique
Martin, Ruben
author_sort Romano, Ciro
collection PubMed
description [Image: see text] A dual catalytic manifold that enables site-selective functionalization of unactivated sp(3) C–O bonds in cyclic acetals with aryl and alkyl halides is reported. The reaction is triggered by an appropriate σ*–p orbital overlap prior to sp(3) C–O cleavage, thus highlighting the importance of conformational flexibility in both reactivity and site selectivity. The protocol is characterized by its excellent chemoselectivity profile, thus offering new vistas for activating strong σ sp(3) C–O linkages.
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spelling pubmed-92643582022-07-09 Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp(3) C–O Bonds in Cyclic Acetals Romano, Ciro Talavera, Laura Gómez-Bengoa, Enrique Martin, Ruben J Am Chem Soc [Image: see text] A dual catalytic manifold that enables site-selective functionalization of unactivated sp(3) C–O bonds in cyclic acetals with aryl and alkyl halides is reported. The reaction is triggered by an appropriate σ*–p orbital overlap prior to sp(3) C–O cleavage, thus highlighting the importance of conformational flexibility in both reactivity and site selectivity. The protocol is characterized by its excellent chemoselectivity profile, thus offering new vistas for activating strong σ sp(3) C–O linkages. American Chemical Society 2022-06-24 2022-07-06 /pmc/articles/PMC9264358/ /pubmed/35749319 http://dx.doi.org/10.1021/jacs.2c04513 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Romano, Ciro
Talavera, Laura
Gómez-Bengoa, Enrique
Martin, Ruben
Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp(3) C–O Bonds in Cyclic Acetals
title Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp(3) C–O Bonds in Cyclic Acetals
title_full Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp(3) C–O Bonds in Cyclic Acetals
title_fullStr Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp(3) C–O Bonds in Cyclic Acetals
title_full_unstemmed Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp(3) C–O Bonds in Cyclic Acetals
title_short Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp(3) C–O Bonds in Cyclic Acetals
title_sort conformational flexibility as a tool for enabling site-selective functionalization of unactivated sp(3) c–o bonds in cyclic acetals
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9264358/
https://www.ncbi.nlm.nih.gov/pubmed/35749319
http://dx.doi.org/10.1021/jacs.2c04513
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