Addition of sulfenic acids to monosubstituted acetylenes: a theoretical and experimental study |
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| Authors: | Maria Chiara Aversa Anna Barattucci Paola Bonaccorsi Alessandro Contini |
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| Affiliation: | 1. Dipartimento di Chimica organica e biologica, Università degli Studi di Messina, Salita Sperone 31 (vill. S. Agata), 98166 Messina, Italy;2. Centro Interuniversitario di Ricerca sulle Reazioni Pericicliche e Sintesi di Sistemi Etero e Carbociclici, Italy;3. Istituto di Chimica organica “A. Marchesini”, Facoltà di Farmacia, Università degli Studi di Milano, Via Venezian 21, 20133 Milano, Italy |
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| Abstract: | The reaction of benzenesulfenic acid, generated in situ by thermal decomposition of 3‐(phenylsulfinyl)propanenitrile, with monosubstituted acetylenes was experimentally and theoretically investigated at the DFT level using the MPW1B95 density functional. A computational model based on the Hard Soft Acid Base (HSAB) principle was evaluated for its ability to qualitatively and quantitatively predict the regioselectivity, while kinetics and thermodynamics of the reaction were studied through the analysis of the reaction paths leading to the possible regioisomers. Copyright © 2009 John Wiley & Sons, Ltd. |
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| Keywords: | DFT HSAB principle regioselectivity sulfenic acids syn‐Addition |
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