Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic N-Acyl Iminium Ions

γ− and δ-Oxoesters are easily available starting materials that have been sparingly used in some organocatalyzed reactions proceeding with a high enantioselectivity. In our experimentation we found that the use of these compounds as the enolizable (nucleophilic) component in organocatalyzed Mannich-...

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Autores principales: Menichetti, Andrea, Di Pietro, Sebastiano, Di Bussolo, Valeria, Favero, Lucilla, Pineschi, Mauro
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2020
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7221655/
https://www.ncbi.nlm.nih.gov/pubmed/32326095
http://dx.doi.org/10.3390/molecules25081903
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author Menichetti, Andrea
Di Pietro, Sebastiano
Di Bussolo, Valeria
Favero, Lucilla
Pineschi, Mauro
author_facet Menichetti, Andrea
Di Pietro, Sebastiano
Di Bussolo, Valeria
Favero, Lucilla
Pineschi, Mauro
author_sort Menichetti, Andrea
collection PubMed
description γ− and δ-Oxoesters are easily available starting materials that have been sparingly used in some organocatalyzed reactions proceeding with a high enantioselectivity. In our experimentation we found that the use of these compounds as the enolizable (nucleophilic) component in organocatalyzed Mannich-type reactions using in situ-generated cyclic N-acyl iminium ions gave low diastereoselectivity and low to moderate values of enantioselectivity. This significant drop of facial selectivity with respect to simple aliphatic aldehydes has been rationalized by means of density functional theory (DFT) calculations.
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spelling pubmed-72216552020-05-22 Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic N-Acyl Iminium Ions Menichetti, Andrea Di Pietro, Sebastiano Di Bussolo, Valeria Favero, Lucilla Pineschi, Mauro Molecules Article γ− and δ-Oxoesters are easily available starting materials that have been sparingly used in some organocatalyzed reactions proceeding with a high enantioselectivity. In our experimentation we found that the use of these compounds as the enolizable (nucleophilic) component in organocatalyzed Mannich-type reactions using in situ-generated cyclic N-acyl iminium ions gave low diastereoselectivity and low to moderate values of enantioselectivity. This significant drop of facial selectivity with respect to simple aliphatic aldehydes has been rationalized by means of density functional theory (DFT) calculations. MDPI 2020-04-20 /pmc/articles/PMC7221655/ /pubmed/32326095 http://dx.doi.org/10.3390/molecules25081903 Text en © 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Menichetti, Andrea
Di Pietro, Sebastiano
Di Bussolo, Valeria
Favero, Lucilla
Pineschi, Mauro
Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic N-Acyl Iminium Ions
title Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic N-Acyl Iminium Ions
title_full Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic N-Acyl Iminium Ions
title_fullStr Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic N-Acyl Iminium Ions
title_full_unstemmed Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic N-Acyl Iminium Ions
title_short Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic N-Acyl Iminium Ions
title_sort experimental and computational studies unraveling the peculiarity of enolizable oxoesters in the organocatalyzed mannich-type addition to cyclic n-acyl iminium ions
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7221655/
https://www.ncbi.nlm.nih.gov/pubmed/32326095
http://dx.doi.org/10.3390/molecules25081903
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