Tandem Hock and Friedel–Crafts reactions allowing an expedient synthesis of a cyclolignan-type scaffold
The Hock cleavage, which is compatible with tandem processes, was applied to the synthesis of 1-aryltetralines through a one-pot transformation from readily available benzyl(prenyl)malonate substrates. After the photooxygenation of the prenyl moiety, the resulting hydroperoxide was directly engaged...
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| Format: | Article |
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Beilstein-Institut
2024-01-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.20.15 |
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| author | Viktoria A. Ikonnikova Cristina Cheibas Oscar Gayraud Alexandra E. Bosnidou Nicolas Casaretto Gilles Frison Bastien Nay |
| author_facet | Viktoria A. Ikonnikova Cristina Cheibas Oscar Gayraud Alexandra E. Bosnidou Nicolas Casaretto Gilles Frison Bastien Nay |
| author_sort | Viktoria A. Ikonnikova |
| collection | DOAJ |
| description | The Hock cleavage, which is compatible with tandem processes, was applied to the synthesis of 1-aryltetralines through a one-pot transformation from readily available benzyl(prenyl)malonate substrates. After the photooxygenation of the prenyl moiety, the resulting hydroperoxide was directly engaged in a Hock cleavage by adding a Lewis acid. The presence of an aromatic nucleophile in the reaction mixture and that of a benzyl moiety on the substrate resulted in tandem Friedel–Crafts reactions to form the 1-aryltetraline products. These compounds share a close analogy to the cyclolignan natural products. Experimental observations and a DFT study support the involvement of an aldehyde intermediate during the Friedel–Crafts reactions, rather than an oxocarbenium. |
| first_indexed | 2024-03-08T05:28:08Z |
| format | Article |
| id | doaj.art-90cd36c8172a4e9a82beed3902be4a6c |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-03-08T05:28:08Z |
| publishDate | 2024-01-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-90cd36c8172a4e9a82beed3902be4a6c2024-02-06T09:08:42ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972024-01-0120116216910.3762/bjoc.20.151860-5397-20-15Tandem Hock and Friedel–Crafts reactions allowing an expedient synthesis of a cyclolignan-type scaffoldViktoria A. Ikonnikova0Cristina Cheibas1Oscar Gayraud2Alexandra E. Bosnidou3Nicolas Casaretto4Gilles Frison5Bastien Nay6Laboratoire de Synthèse Organique, Ecole Polytechnique, CNRS, ENSTA, Institut Polytechnique de Paris, F-91128 Palaiseau, France Laboratoire de Synthèse Organique, Ecole Polytechnique, CNRS, ENSTA, Institut Polytechnique de Paris, F-91128 Palaiseau, France Laboratoire de Synthèse Organique, Ecole Polytechnique, CNRS, ENSTA, Institut Polytechnique de Paris, F-91128 Palaiseau, France Laboratoire de Synthèse Organique, Ecole Polytechnique, CNRS, ENSTA, Institut Polytechnique de Paris, F-91128 Palaiseau, France Laboratoire de Chimie Moléculaire, Ecole Polytechnique, CNRS, Institut Polytechnique de Paris, F-91128 Palaiseau, France Sorbonne Université, CNRS, Laboratoire de Chimie Théorique, 75005 Paris, France Laboratoire de Synthèse Organique, Ecole Polytechnique, CNRS, ENSTA, Institut Polytechnique de Paris, F-91128 Palaiseau, France The Hock cleavage, which is compatible with tandem processes, was applied to the synthesis of 1-aryltetralines through a one-pot transformation from readily available benzyl(prenyl)malonate substrates. After the photooxygenation of the prenyl moiety, the resulting hydroperoxide was directly engaged in a Hock cleavage by adding a Lewis acid. The presence of an aromatic nucleophile in the reaction mixture and that of a benzyl moiety on the substrate resulted in tandem Friedel–Crafts reactions to form the 1-aryltetraline products. These compounds share a close analogy to the cyclolignan natural products. Experimental observations and a DFT study support the involvement of an aldehyde intermediate during the Friedel–Crafts reactions, rather than an oxocarbenium.https://doi.org/10.3762/bjoc.20.151-aryltetralinesfriedel–crafts reactionhock rearrangementoxidative cleavagetandem reactions |
| spellingShingle | Viktoria A. Ikonnikova Cristina Cheibas Oscar Gayraud Alexandra E. Bosnidou Nicolas Casaretto Gilles Frison Bastien Nay Tandem Hock and Friedel–Crafts reactions allowing an expedient synthesis of a cyclolignan-type scaffold Beilstein Journal of Organic Chemistry 1-aryltetralines friedel–crafts reaction hock rearrangement oxidative cleavage tandem reactions |
| title | Tandem Hock and Friedel–Crafts reactions allowing an expedient synthesis of a cyclolignan-type scaffold |
| title_full | Tandem Hock and Friedel–Crafts reactions allowing an expedient synthesis of a cyclolignan-type scaffold |
| title_fullStr | Tandem Hock and Friedel–Crafts reactions allowing an expedient synthesis of a cyclolignan-type scaffold |
| title_full_unstemmed | Tandem Hock and Friedel–Crafts reactions allowing an expedient synthesis of a cyclolignan-type scaffold |
| title_short | Tandem Hock and Friedel–Crafts reactions allowing an expedient synthesis of a cyclolignan-type scaffold |
| title_sort | tandem hock and friedel crafts reactions allowing an expedient synthesis of a cyclolignan type scaffold |
| topic | 1-aryltetralines friedel–crafts reaction hock rearrangement oxidative cleavage tandem reactions |
| url | https://doi.org/10.3762/bjoc.20.15 |
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