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

A general strategy for the synthesis of 2-substituted cyclobutanone sulfides via a tandem Bronsted 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 yi...

Full description

Saved in:
Bibliographic Details
Published inSynthesis (Stuttgart) Vol. 54; no. 24; pp. 5423 - 5433
Main Authors Porcu, Stefania, Cabua, Maria Chiara, Velichko, Viktoria, Baltaze, Jean-Pierre, Frongia, Angelo, Carbonaro, Carlo Maria, Ricci, Pier Carlo, Parsons, Drew Francis, Carlone, Armando, Secci, Francesco
Format Journal Article
LanguageEnglish
Published STUTTGART Thieme Medical Publishers 15.12.2022
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
transposition
CYCLOBUTANE DERIVATIVES
ACID
Bronsted acid catalysis
ring expansion
ALDOL REACTION
cyclobutanones
USEFUL SYNTHONS
thiols
ring contraction
quantum chemical DFT
Online AccessGet more information

Cover

More Information
Summary:A general strategy for the synthesis of 2-substituted cyclobutanone sulfides via a tandem Bronsted 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.
ISSN:0039-7881
1437-210X
DOI:10.1055/a-1912-1096