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Insights into the Reactivity of 2-Hydroxycyclobutanones with Thiols Corroborated by Quantum Chemical DFT Investigations and NMR and Raman Analysis

Authors :
Francesco Secci
Armando Carlone
Stefania Porcu
Maria Chiara Cabua
Viktoria Velichko
Jean-Pierre Baltaze
Angelo Frongia
Carlo Maria Carbonaro
Pier Carlo Ricci
Drew Francis Parsons
Source :
Synthesis. 54:5423-5433
Publication Year :
2022
Publisher :
Georg Thieme Verlag KG, 2022.

Abstract

A general strategy for the synthesis of 2-substituted cyclobutanone sulfides via a tandem Brønsted acid-catalyzed nucleophile addition/ring contraction/C3-C4 ring expansion reaction sequence has been exploited. The procedure led to a wide panel of four-membered cyclic ketones in good to excellent yields and with broad substrate scope. Mechanistic aspects and kinetic parameters were investigated by quantum chemical DFT calculations, allowing us to rationalize the different reactivity of 2-aryl- and 2-alkyl-substituted 2-hydroxycyclobutanones towards thiol nucleophiles in reactions mediated by sulfonic acids. NMR and in situ Raman techniques were employed to better understand the reaction kinetics and parameters that affect the desired outcome.

Subjects

Subjects :
Organic Chemistry
Catalysis

Details

ISSN :
1437210X and 00397881
Volume :
54
Database :
OpenAIRE
Journal :
Synthesis
Accession number :
edsair.doi.dedup.....c071090d2ee9eb33ab92d0624a5fe545