Reactivity of Imidazole‐ and Pyridine‐Carboxaldehydes for Gem‐Diol and Hemiacetal Generation: Theoretical and Experimental Insights
Abstract Gem‐diols are defined as organic molecules carrying two hydroxyl groups at the same carbon atom, which is the result of the nucleophilic addition of water to a carbonyl group. In this work, the generation of the hydrated or hemiacetal forms using pyridine‐ and imidazole‐carboxaldehyde isome...
Saved in:
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley-VCH
2025-08-01
|
| Series: | ChemistryOpen |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/open.202400411 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1849230107335458816 |
|---|---|
| author | Ayelén F. Crespi Emiliano Barrionuevo Gabriel Jasinski Albertina G. Moglioni Daniel Vega Juan M. Lázaro‐Martínez |
| author_facet | Ayelén F. Crespi Emiliano Barrionuevo Gabriel Jasinski Albertina G. Moglioni Daniel Vega Juan M. Lázaro‐Martínez |
| author_sort | Ayelén F. Crespi |
| collection | DOAJ |
| description | Abstract Gem‐diols are defined as organic molecules carrying two hydroxyl groups at the same carbon atom, which is the result of the nucleophilic addition of water to a carbonyl group. In this work, the generation of the hydrated or hemiacetal forms using pyridine‐ and imidazole‐carboxaldehyde isomers in different chemical environments was studied by Nuclear Magnetic Resonance (NMR) recorded in different media and combined with theoretical calculations. The change in the position of aldehyde group in either the pyridine or the imidazole ring had a clear effect in the course of the hydration/hemiacetal generation reaction, which was favored in protic solvents mainly in the presence of methanol. For pyridinecarboxaldehydes, the acidity/basicity degree of the reaction medium influenced not only the generation of the gem‐diol or hemiacetal forms but also the oxidation to the corresponding carboxylic acid. However, imidazolecarboxaldehyde was found to be less reactive to the nucleophilic addition of water and methanol than the other compounds in all the environments evaluated. Furthermore, both the gem‐diol/hemiacetal generation and the Cannizzaro reaction products were studied in alkaline medium. |
| format | Article |
| id | doaj-art-aedcc975bb2d42559898ed6fa363a08f |
| institution | Kabale University |
| issn | 2191-1363 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryOpen |
| spelling | doaj-art-aedcc975bb2d42559898ed6fa363a08f2025-08-21T12:05:32ZengWiley-VCHChemistryOpen2191-13632025-08-01148n/an/a10.1002/open.202400411Reactivity of Imidazole‐ and Pyridine‐Carboxaldehydes for Gem‐Diol and Hemiacetal Generation: Theoretical and Experimental InsightsAyelén F. Crespi0Emiliano Barrionuevo1Gabriel Jasinski2Albertina G. Moglioni3Daniel Vega4Juan M. Lázaro‐Martínez5Universidad de Buenos Aires Facultad de Farmacia y Bioquímica Department of Chemistry Ciudad Autónoma de Buenos Aires 1113 ArgentinaCONICET – Universidad de Buenos Aires Instituto de Química y Metabolismo del Fármaco (IQUIMEFA-UBA-CONICET) Ciudad Autónoma de Buenos Aires 1113 ArgentinaCONICET – Universidad de Buenos Aires Instituto de Química y Metabolismo del Fármaco (IQUIMEFA-UBA-CONICET) Ciudad Autónoma de Buenos Aires 1113 ArgentinaCONICET – Universidad de Buenos Aires Instituto de Química y Metabolismo del Fármaco (IQUIMEFA-UBA-CONICET) Ciudad Autónoma de Buenos Aires 1113 ArgentinaDepartment of Condensed Matter Physics Comisión Nacional de Energía Atómica San Martín, Buenos Aires 1650 ArgentinaUniversidad de Buenos Aires Facultad de Farmacia y Bioquímica Department of Chemistry Ciudad Autónoma de Buenos Aires 1113 ArgentinaAbstract Gem‐diols are defined as organic molecules carrying two hydroxyl groups at the same carbon atom, which is the result of the nucleophilic addition of water to a carbonyl group. In this work, the generation of the hydrated or hemiacetal forms using pyridine‐ and imidazole‐carboxaldehyde isomers in different chemical environments was studied by Nuclear Magnetic Resonance (NMR) recorded in different media and combined with theoretical calculations. The change in the position of aldehyde group in either the pyridine or the imidazole ring had a clear effect in the course of the hydration/hemiacetal generation reaction, which was favored in protic solvents mainly in the presence of methanol. For pyridinecarboxaldehydes, the acidity/basicity degree of the reaction medium influenced not only the generation of the gem‐diol or hemiacetal forms but also the oxidation to the corresponding carboxylic acid. However, imidazolecarboxaldehyde was found to be less reactive to the nucleophilic addition of water and methanol than the other compounds in all the environments evaluated. Furthermore, both the gem‐diol/hemiacetal generation and the Cannizzaro reaction products were studied in alkaline medium.https://doi.org/10.1002/open.202400411PyridinecarboxaldehydesImidazolecarboxaldehydesNMRGem-diolTheoretical calculations |
| spellingShingle | Ayelén F. Crespi Emiliano Barrionuevo Gabriel Jasinski Albertina G. Moglioni Daniel Vega Juan M. Lázaro‐Martínez Reactivity of Imidazole‐ and Pyridine‐Carboxaldehydes for Gem‐Diol and Hemiacetal Generation: Theoretical and Experimental Insights ChemistryOpen Pyridinecarboxaldehydes Imidazolecarboxaldehydes NMR Gem-diol Theoretical calculations |
| title | Reactivity of Imidazole‐ and Pyridine‐Carboxaldehydes for Gem‐Diol and Hemiacetal Generation: Theoretical and Experimental Insights |
| title_full | Reactivity of Imidazole‐ and Pyridine‐Carboxaldehydes for Gem‐Diol and Hemiacetal Generation: Theoretical and Experimental Insights |
| title_fullStr | Reactivity of Imidazole‐ and Pyridine‐Carboxaldehydes for Gem‐Diol and Hemiacetal Generation: Theoretical and Experimental Insights |
| title_full_unstemmed | Reactivity of Imidazole‐ and Pyridine‐Carboxaldehydes for Gem‐Diol and Hemiacetal Generation: Theoretical and Experimental Insights |
| title_short | Reactivity of Imidazole‐ and Pyridine‐Carboxaldehydes for Gem‐Diol and Hemiacetal Generation: Theoretical and Experimental Insights |
| title_sort | reactivity of imidazole and pyridine carboxaldehydes for gem diol and hemiacetal generation theoretical and experimental insights |
| topic | Pyridinecarboxaldehydes Imidazolecarboxaldehydes NMR Gem-diol Theoretical calculations |
| url | https://doi.org/10.1002/open.202400411 |
| work_keys_str_mv | AT ayelenfcrespi reactivityofimidazoleandpyridinecarboxaldehydesforgemdiolandhemiacetalgenerationtheoreticalandexperimentalinsights AT emilianobarrionuevo reactivityofimidazoleandpyridinecarboxaldehydesforgemdiolandhemiacetalgenerationtheoreticalandexperimentalinsights AT gabrieljasinski reactivityofimidazoleandpyridinecarboxaldehydesforgemdiolandhemiacetalgenerationtheoreticalandexperimentalinsights AT albertinagmoglioni reactivityofimidazoleandpyridinecarboxaldehydesforgemdiolandhemiacetalgenerationtheoreticalandexperimentalinsights AT danielvega reactivityofimidazoleandpyridinecarboxaldehydesforgemdiolandhemiacetalgenerationtheoreticalandexperimentalinsights AT juanmlazaromartinez reactivityofimidazoleandpyridinecarboxaldehydesforgemdiolandhemiacetalgenerationtheoreticalandexperimentalinsights |