Oxidant-free annulation of α-hydroxy ketones with diamines using aluminum(III) chloride: A supramolecular approach for practical quinoxaline synthesis
The conventional reaction of α-hydroxy ketones (acyloins) with arene-1,2-diamines typically requires an oxidant to facilitate a tandem oxidative condensation, resulting in quinoxaline derivatives. In this study, an innovative approach has been introduced that eliminates the need for an oxidant, serv...
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Elsevier
2025-03-01
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| Series: | Results in Chemistry |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2211715625001316 |
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| author | Maryam Farajpour Mojdehi Hani Sayahi Saeed K. Amini Farshid Mohsenzadeh Hossein Reza Darabi Kioumars Aghapoor |
| author_facet | Maryam Farajpour Mojdehi Hani Sayahi Saeed K. Amini Farshid Mohsenzadeh Hossein Reza Darabi Kioumars Aghapoor |
| author_sort | Maryam Farajpour Mojdehi |
| collection | DOAJ |
| description | The conventional reaction of α-hydroxy ketones (acyloins) with arene-1,2-diamines typically requires an oxidant to facilitate a tandem oxidative condensation, resulting in quinoxaline derivatives. In this study, an innovative approach has been introduced that eliminates the need for an oxidant, serving as an alternative to tandem oxidative protocols. Inspired by the ability of 3-hydroxyflavones to chelate Al(III) ions, this study focused on exploring the self-activation of acyloins with AlCl3 in the oxidant-free synthesis of quinoxalines via the formation of the acyloin@AlCl3 complex. Thus, when aromatic 1,2-diamines were exposed to the activated acyloin@AlCl3 complex under ethanolic conditions, high to excellent yields of quinoxalines were achieved. Additionally, the effect of other metal chlorides on the reaction was systematically investigated. To elucidate the specific role of aluminum(III) chloride in the annulation process, density functional theory was employed to show that the benzoin is activated in the presence of AlCl3 for further condensation reaction. Experimental validation of the model reaction, conducted through cyclic voltammetry corroborated the theoretical findings, demonstrating that benzoin exhibits greater electrochemical activity than benzene-1,2-diamine (ortho-PD) in the presence of AlCl3. Collectively, these data revealed the self-activation of benzoin as the host through the incorporation of AlCl3 as the guest. |
| format | Article |
| id | doaj-art-79b80dc7d65d41e8a254c3d44a90cd22 |
| institution | DOAJ |
| issn | 2211-7156 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Results in Chemistry |
| spelling | doaj-art-79b80dc7d65d41e8a254c3d44a90cd222025-08-20T02:56:51ZengElsevierResults in Chemistry2211-71562025-03-011410214810.1016/j.rechem.2025.102148Oxidant-free annulation of α-hydroxy ketones with diamines using aluminum(III) chloride: A supramolecular approach for practical quinoxaline synthesisMaryam Farajpour Mojdehi0Hani Sayahi1Saeed K. Amini2Farshid Mohsenzadeh3Hossein Reza Darabi4Kioumars Aghapoor5Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151, IranCorresponding author.; Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151, IranChemistry and Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151, IranChemistry and Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151, IranChemistry and Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151, IranChemistry and Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151, IranThe conventional reaction of α-hydroxy ketones (acyloins) with arene-1,2-diamines typically requires an oxidant to facilitate a tandem oxidative condensation, resulting in quinoxaline derivatives. In this study, an innovative approach has been introduced that eliminates the need for an oxidant, serving as an alternative to tandem oxidative protocols. Inspired by the ability of 3-hydroxyflavones to chelate Al(III) ions, this study focused on exploring the self-activation of acyloins with AlCl3 in the oxidant-free synthesis of quinoxalines via the formation of the acyloin@AlCl3 complex. Thus, when aromatic 1,2-diamines were exposed to the activated acyloin@AlCl3 complex under ethanolic conditions, high to excellent yields of quinoxalines were achieved. Additionally, the effect of other metal chlorides on the reaction was systematically investigated. To elucidate the specific role of aluminum(III) chloride in the annulation process, density functional theory was employed to show that the benzoin is activated in the presence of AlCl3 for further condensation reaction. Experimental validation of the model reaction, conducted through cyclic voltammetry corroborated the theoretical findings, demonstrating that benzoin exhibits greater electrochemical activity than benzene-1,2-diamine (ortho-PD) in the presence of AlCl3. Collectively, these data revealed the self-activation of benzoin as the host through the incorporation of AlCl3 as the guest.http://www.sciencedirect.com/science/article/pii/S2211715625001316Oxidant-free reactionSupramolecular catalysisSelf-activation of acyloinQuinoxalineDensity functional theoryCyclic voltammetry |
| spellingShingle | Maryam Farajpour Mojdehi Hani Sayahi Saeed K. Amini Farshid Mohsenzadeh Hossein Reza Darabi Kioumars Aghapoor Oxidant-free annulation of α-hydroxy ketones with diamines using aluminum(III) chloride: A supramolecular approach for practical quinoxaline synthesis Results in Chemistry Oxidant-free reaction Supramolecular catalysis Self-activation of acyloin Quinoxaline Density functional theory Cyclic voltammetry |
| title | Oxidant-free annulation of α-hydroxy ketones with diamines using aluminum(III) chloride: A supramolecular approach for practical quinoxaline synthesis |
| title_full | Oxidant-free annulation of α-hydroxy ketones with diamines using aluminum(III) chloride: A supramolecular approach for practical quinoxaline synthesis |
| title_fullStr | Oxidant-free annulation of α-hydroxy ketones with diamines using aluminum(III) chloride: A supramolecular approach for practical quinoxaline synthesis |
| title_full_unstemmed | Oxidant-free annulation of α-hydroxy ketones with diamines using aluminum(III) chloride: A supramolecular approach for practical quinoxaline synthesis |
| title_short | Oxidant-free annulation of α-hydroxy ketones with diamines using aluminum(III) chloride: A supramolecular approach for practical quinoxaline synthesis |
| title_sort | oxidant free annulation of α hydroxy ketones with diamines using aluminum iii chloride a supramolecular approach for practical quinoxaline synthesis |
| topic | Oxidant-free reaction Supramolecular catalysis Self-activation of acyloin Quinoxaline Density functional theory Cyclic voltammetry |
| url | http://www.sciencedirect.com/science/article/pii/S2211715625001316 |
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