The resorcin[4]arene capsule was found to catalyze β-selective furanosylation reactions for a variety of different furanosyl donors: α-d- and α-l-arabinosyl-, α-l-fucosyl-, α-d-ribosyl-, α-d-xylosyl-, and even α-d-lyxosyl fluorides. The scope is only limited by the inherently finite volume inside the closed capsular catalyst. The catalyst is readily available on a multi-100 g scale and can be recycled for at least seven rounds without significant loss in activity, yield, and selectivity. The mechanistic investigations indicated that the furanosylation mechanism is shifted toward an SN1 reaction on the mechanistic continuum between the prototypical SN1 and SN2 substitution types, as compared to the pyranosylation reaction inside the same catalyst. This is especially true for the lyxosyl donor, as indicated by the nucleophile reaction order of 0.26, and supported by metadynamics calculations. The mechanistic shift toward SN1 is of high interest as it indicates that this catalyst not only enables β-selective furanosylations and pyranoslyations independently of the substrate configuration but in addition also independently of the operating mechanism. To our knowledge, there is no alternative catalyst available that displays such properties.

Supramolecular Capsule-Catalyzed Highly β-Selective Furanosylation Independent of the SN1/SN2 Reaction Pathway / Li, T. -R.; Piccini, G.; Tiefenbacher, K.. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 145:7(2022), pp. 4294-4303. [10.1021/jacs.2c13641]

Supramolecular Capsule-Catalyzed Highly β-Selective Furanosylation Independent of the SN1/SN2 Reaction Pathway

Piccini G.;
2022

Abstract

The resorcin[4]arene capsule was found to catalyze β-selective furanosylation reactions for a variety of different furanosyl donors: α-d- and α-l-arabinosyl-, α-l-fucosyl-, α-d-ribosyl-, α-d-xylosyl-, and even α-d-lyxosyl fluorides. The scope is only limited by the inherently finite volume inside the closed capsular catalyst. The catalyst is readily available on a multi-100 g scale and can be recycled for at least seven rounds without significant loss in activity, yield, and selectivity. The mechanistic investigations indicated that the furanosylation mechanism is shifted toward an SN1 reaction on the mechanistic continuum between the prototypical SN1 and SN2 substitution types, as compared to the pyranosylation reaction inside the same catalyst. This is especially true for the lyxosyl donor, as indicated by the nucleophile reaction order of 0.26, and supported by metadynamics calculations. The mechanistic shift toward SN1 is of high interest as it indicates that this catalyst not only enables β-selective furanosylations and pyranoslyations independently of the substrate configuration but in addition also independently of the operating mechanism. To our knowledge, there is no alternative catalyst available that displays such properties.
2022
145
7
4294
4303
Supramolecular Capsule-Catalyzed Highly β-Selective Furanosylation Independent of the SN1/SN2 Reaction Pathway / Li, T. -R.; Piccini, G.; Tiefenbacher, K.. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 145:7(2022), pp. 4294-4303. [10.1021/jacs.2c13641]
Li, T. -R.; Piccini, G.; Tiefenbacher, K.
File in questo prodotto:
File Dimensione Formato  
li-et-al-2023-supramolecular-capsule-catalyzed-highly-β-selective-furanosylation-independent-of-the-sn1-sn2-reaction.pdf

Accesso riservato

Tipologia: Versione pubblicata dall'editore
Dimensione 3.71 MB
Formato Adobe PDF
3.71 MB Adobe PDF   Visualizza/Apri   Richiedi una copia
Pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/1330715
Citazioni
  • ???jsp.display-item.citation.pmc??? 1
  • Scopus 5
  • ???jsp.display-item.citation.isi??? 4
social impact