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DOI: 10.1055/a-1912-1096
Insights into the Reactivity of 2-Hydroxycyclobutanones with Thiols Corroborated by Quantum Chemical DFT Investigations and NMR and Raman Analysis
We gratefully acknowledge funding from the Fondazione di Sardegna (CUP F71I17000180002).
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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.
Key words
cyclobutanones - thiols - ring contraction - ring expansion - Brønsted acid catalysis - transposition - quantum chemical DFTSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1912-1096.
- Supporting Information
Publication History
Received: 30 June 2022
Accepted after revision: 28 July 2022
Accepted Manuscript online:
28 July 2022
Article published online:
10 October 2022
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