Theoretical and Experimental Insights into the Tandem Mannich—Electrophilic Amination Reaction: Synthesis of Safirinium Dyes
Isoxazolo[3,4-<i>b</i>]pyridin-3(1<i>H</i>)-ones are ‘spring-loaded’ compounds that quantitatively react with iminium salts derived from formaldehyde and secondary amines to yield fluorescent Safirinium dyes. The mechanism and energetics of the above tandem Mannich–electrophi...
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| Online Access: | https://www.mdpi.com/2076-3417/11/12/5498 |
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doaj-51398cbc02fd4493896d7e74bcc3f8182021-07-01T00:07:48ZengMDPI AGApplied Sciences2076-34172021-06-01115498549810.3390/app11125498Theoretical and Experimental Insights into the Tandem Mannich—Electrophilic Amination Reaction: Synthesis of Safirinium DyesJarosław Sączewski0Joanna Fedorowicz1Paulina Wiśniewska2Maria Gdaniec3Department of Organic Chemistry, Faculty of Pharmacy, Medical University of Gdansk, 107 Gen. J. Hallera Av., 80-416 Gdansk, PolandDepartment of Chemical Technology of Drugs, Faculty of Pharmacy, Medical University of Gdansk, 107 Gen. J. Hallera Av., 80-416 Gdansk, PolandDepartment of Organic Chemistry, Faculty of Pharmacy, Medical University of Gdansk, 107 Gen. J. Hallera Av., 80-416 Gdansk, PolandFaculty of Chemistry, Adam Mickiewicz University, 61-614 Poznan, PolandIsoxazolo[3,4-<i>b</i>]pyridin-3(1<i>H</i>)-ones are ‘spring-loaded’ compounds that quantitatively react with iminium salts derived from formaldehyde and secondary amines to yield fluorescent Safirinium dyes. The mechanism and energetics of the above tandem Mannich–electrophilic amination reaction have been investigated experimentally and using theoretical methods. The hybrid B3LYP functional with GD3 empirical dispersion and range-separated hybrid functional ωB97XD, both combined with a PCM model, were applied to acquire the energetic profiles of the studied reaction with respect to the structure of secondary amine and isoxazolone used. Diastereoselectivity of the tandem reactions involving iminium salt derived from L-proline has been rationalized theoretically by means of density functional theory calculations.https://www.mdpi.com/2076-3417/11/12/5498cationic dyesDFTelectrophilic aminationisoxazoloneMannich reactionspring-loaded reactants |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Jarosław Sączewski Joanna Fedorowicz Paulina Wiśniewska Maria Gdaniec |
| spellingShingle |
Jarosław Sączewski Joanna Fedorowicz Paulina Wiśniewska Maria Gdaniec Theoretical and Experimental Insights into the Tandem Mannich—Electrophilic Amination Reaction: Synthesis of Safirinium Dyes Applied Sciences cationic dyes DFT electrophilic amination isoxazolone Mannich reaction spring-loaded reactants |
| author_facet |
Jarosław Sączewski Joanna Fedorowicz Paulina Wiśniewska Maria Gdaniec |
| author_sort |
Jarosław Sączewski |
| title |
Theoretical and Experimental Insights into the Tandem Mannich—Electrophilic Amination Reaction: Synthesis of Safirinium Dyes |
| title_short |
Theoretical and Experimental Insights into the Tandem Mannich—Electrophilic Amination Reaction: Synthesis of Safirinium Dyes |
| title_full |
Theoretical and Experimental Insights into the Tandem Mannich—Electrophilic Amination Reaction: Synthesis of Safirinium Dyes |
| title_fullStr |
Theoretical and Experimental Insights into the Tandem Mannich—Electrophilic Amination Reaction: Synthesis of Safirinium Dyes |
| title_full_unstemmed |
Theoretical and Experimental Insights into the Tandem Mannich—Electrophilic Amination Reaction: Synthesis of Safirinium Dyes |
| title_sort |
theoretical and experimental insights into the tandem mannich—electrophilic amination reaction: synthesis of safirinium dyes |
| publisher |
MDPI AG |
| series |
Applied Sciences |
| issn |
2076-3417 |
| publishDate |
2021-06-01 |
| description |
Isoxazolo[3,4-<i>b</i>]pyridin-3(1<i>H</i>)-ones are ‘spring-loaded’ compounds that quantitatively react with iminium salts derived from formaldehyde and secondary amines to yield fluorescent Safirinium dyes. The mechanism and energetics of the above tandem Mannich–electrophilic amination reaction have been investigated experimentally and using theoretical methods. The hybrid B3LYP functional with GD3 empirical dispersion and range-separated hybrid functional ωB97XD, both combined with a PCM model, were applied to acquire the energetic profiles of the studied reaction with respect to the structure of secondary amine and isoxazolone used. Diastereoselectivity of the tandem reactions involving iminium salt derived from L-proline has been rationalized theoretically by means of density functional theory calculations. |
| topic |
cationic dyes DFT electrophilic amination isoxazolone Mannich reaction spring-loaded reactants |
| url |
https://www.mdpi.com/2076-3417/11/12/5498 |
| work_keys_str_mv |
AT jarosławsaczewski theoreticalandexperimentalinsightsintothetandemmannichelectrophilicaminationreactionsynthesisofsafiriniumdyes AT joannafedorowicz theoreticalandexperimentalinsightsintothetandemmannichelectrophilicaminationreactionsynthesisofsafiriniumdyes AT paulinawisniewska theoreticalandexperimentalinsightsintothetandemmannichelectrophilicaminationreactionsynthesisofsafiriniumdyes AT mariagdaniec theoreticalandexperimentalinsightsintothetandemmannichelectrophilicaminationreactionsynthesisofsafiriniumdyes |
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1721349445992316928 |