Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic <i>N</i>-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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MDPI AG
2020-04-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/8/1903 |
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| author | Andrea Menichetti Sebastiano Di Pietro Valeria Di Bussolo Lucilla Favero Mauro Pineschi |
| author_facet | Andrea Menichetti Sebastiano Di Pietro Valeria Di Bussolo Lucilla Favero Mauro Pineschi |
| author_sort | Andrea Menichetti |
| collection | DOAJ |
| 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 <i>N</i>-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. |
| first_indexed | 2024-03-10T20:19:54Z |
| format | Article |
| id | doaj.art-02f6a31101ed493fa30aeb99b90e6cf9 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T20:19:54Z |
| publishDate | 2020-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-02f6a31101ed493fa30aeb99b90e6cf92023-11-19T22:12:56ZengMDPI AGMolecules1420-30492020-04-01258190310.3390/molecules25081903Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic <i>N</i>-Acyl Iminium IonsAndrea Menichetti0Sebastiano Di Pietro1Valeria Di Bussolo2Lucilla Favero3Mauro Pineschi4Department of Pharmacy, University of Pisa, via Bonanno 33, 56126 Pisa, ItalyDepartment of Pharmacy, University of Pisa, via Bonanno 33, 56126 Pisa, ItalyDepartment of Chemistry and Industrial Chemistry, University of Pisa, via Moruzzi 3, 56124 Pisa, ItalyDepartment of Pharmacy, University of Pisa, via Bonanno 33, 56126 Pisa, ItalyDepartment of Pharmacy, University of Pisa, via Bonanno 33, 56126 Pisa, Italyγ− 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 <i>N</i>-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.https://www.mdpi.com/1420-3049/25/8/1903<i>N</i>,<i>O</i>-acetalsorganocatalysisoxoestersMannich reactionsDFT studyheteroaryl lactones |
| spellingShingle | Andrea Menichetti Sebastiano Di Pietro Valeria Di Bussolo Lucilla Favero Mauro Pineschi Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic <i>N</i>-Acyl Iminium Ions Molecules <i>N</i>,<i>O</i>-acetals organocatalysis oxoesters Mannich reactions DFT study heteroaryl lactones |
| title | Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic <i>N</i>-Acyl Iminium Ions |
| title_full | Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic <i>N</i>-Acyl Iminium Ions |
| title_fullStr | Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic <i>N</i>-Acyl Iminium Ions |
| title_full_unstemmed | Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic <i>N</i>-Acyl Iminium Ions |
| title_short | Experimental and Computational Studies Unraveling the Peculiarity of Enolizable Oxoesters in the Organocatalyzed Mannich-Type Addition to Cyclic <i>N</i>-Acyl Iminium Ions |
| title_sort | experimental and computational studies unraveling the peculiarity of enolizable oxoesters in the organocatalyzed mannich type addition to cyclic i n i acyl iminium ions |
| topic | <i>N</i>,<i>O</i>-acetals organocatalysis oxoesters Mannich reactions DFT study heteroaryl lactones |
| url | https://www.mdpi.com/1420-3049/25/8/1903 |
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