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Lactone Enolates of Isochroman-3-ones and 2-Coumaranones: Quantification of Their Nucleophilicity in DMSO and Conjugate Additions to Chalcones.
Mousavi, Mohammad Sadeq; Di Mola, Antonia; Pierri, Giovanni; Tedesco, Consiglia; Hensinger, Magenta J; Sun, Aijia; Wang, Yilan; Mayer, Peter; Ofial, Armin R; Massa, Antonio.
Afiliación
  • Mousavi MS; Dipartimento di Chimica e Biologia "A. Zambelli", Università degli Studi di Salerno, Via Giovanni Paolo II, 84084 Fisciano, SA, Italy.
  • Di Mola A; Dipartimento di Chimica e Biologia "A. Zambelli", Università degli Studi di Salerno, Via Giovanni Paolo II, 84084 Fisciano, SA, Italy.
  • Pierri G; Dipartimento di Chimica e Biologia "A. Zambelli", Università degli Studi di Salerno, Via Giovanni Paolo II, 84084 Fisciano, SA, Italy.
  • Tedesco C; Dipartimento di Chimica e Biologia "A. Zambelli", Università degli Studi di Salerno, Via Giovanni Paolo II, 84084 Fisciano, SA, Italy.
  • Hensinger MJ; Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München, Germany.
  • Sun A; Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München, Germany.
  • Wang Y; Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München, Germany.
  • Mayer P; Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München, Germany.
  • Ofial AR; Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München, Germany.
  • Massa A; Dipartimento di Chimica e Biologia "A. Zambelli", Università degli Studi di Salerno, Via Giovanni Paolo II, 84084 Fisciano, SA, Italy.
J Org Chem ; 89(10): 6915-6928, 2024 May 17.
Article en En | MEDLINE | ID: mdl-38687827
ABSTRACT
Owing to stereoelectronic effects, lactones often deviate in reactivity from their open-chain ester analogues as demonstrated by the CH acidity (in DMSO) of 3-isochromanone (pKa = 18.8) and 2-coumaranone (pKa = 13.5), which is higher than that of ethyl phenylacetate (pKa = 22.6). We have now characterized the reactivity of the lactone enolates derived from 3-isochromanone and 2-coumaranone by following the kinetics of their Michael reactions with p-quinone methides and arylidenemalonates (reference electrophiles) in DMSO at 20 °C. Evaluation of the experimentally determined second-order rate constants k2 by the Mayr-Patz equation, lg k2 = sN(N + E), furnished the nucleophilicity parameters N (and sN) of the lactone enolates. By localizing their position on the Mayr nucleophilicity scale, the scope of their electrophilic reaction partners becomes predictable, and we demonstrate a novel catalytic methodology for a series of carbon-carbon bond-forming reactions of lactone enolates with chalcones under phase transfer conditions in toluene.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Org Chem Año: 2024 Tipo del documento: Article País de afiliación: Italia Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Org Chem Año: 2024 Tipo del documento: Article País de afiliación: Italia Pais de publicación: Estados Unidos