Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple
A reliable method for the synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexanes through the 1,3-dipolar cycloaddition (1,3-DC) reactions of cyclopropenes to the stable azomethine ylide – protonated form of Ruhemann's purple (PRP) has been developed. Both 3-substituted and 3,3-d...
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Beilstein-Institut
2022-06-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.18.77 |
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| author | Alexander S. Filatov Olesya V. Khoroshilova Anna G. Larina Vitali M. Boitsov Alexander V. Stepakov |
| author_facet | Alexander S. Filatov Olesya V. Khoroshilova Anna G. Larina Vitali M. Boitsov Alexander V. Stepakov |
| author_sort | Alexander S. Filatov |
| collection | DOAJ |
| description | A reliable method for the synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexanes through the 1,3-dipolar cycloaddition (1,3-DC) reactions of cyclopropenes to the stable azomethine ylide – protonated form of Ruhemann's purple (PRP) has been developed. Both 3-substituted and 3,3-disubstituted cyclopropenes reacted with PRP, affording the corresponding bis-spirocyclic 3-azabicyclo[3.1.0]hexane cycloadducts in moderate to good yields with high diastereofacial selectivity. Moreover, several unstable 1,2-disubstituted cyclopropenes were successfully trapped by the stable 1,3-dipole under mild conditions. The mechanism of the cycloaddition reactions of cyclopropenes with PRP has been thoroughly studied using density functional theory (DFT) methods at the M11/cc-pVDZ level of theory. The cycloaddition reactions have been found to be HOMOcyclopropene–LUMOylide controlled while the transition-state energies for the reaction of 3-methyl-3-phenylcyclopropene with PRP are fully consistent with the experimentally observed stereoselectivity. |
| first_indexed | 2024-12-11T18:36:25Z |
| format | Article |
| id | doaj.art-b7994700dee04723b3cff0ae03d87333 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-11T18:36:25Z |
| publishDate | 2022-06-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-b7994700dee04723b3cff0ae03d873332022-12-22T00:54:44ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972022-06-0118176978010.3762/bjoc.18.771860-5397-18-77Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purpleAlexander S. Filatov0Olesya V. Khoroshilova1Anna G. Larina2Vitali M. Boitsov3Alexander V. Stepakov4Saint-Petersburg State University, Universitetskaya nab. 7/9, 199034, St. Petersburg, Russian Federation Saint-Petersburg State University, Universitetskaya nab. 7/9, 199034, St. Petersburg, Russian Federation Saint-Petersburg State University, Universitetskaya nab. 7/9, 199034, St. Petersburg, Russian Federation Saint-Petersburg National Research Academic University of the Russian Academy of Sciences, ul. Khlopina 8/3, 194021, St. Petersburg, Russian Federation Saint-Petersburg State University, Universitetskaya nab. 7/9, 199034, St. Petersburg, Russian Federation A reliable method for the synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexanes through the 1,3-dipolar cycloaddition (1,3-DC) reactions of cyclopropenes to the stable azomethine ylide – protonated form of Ruhemann's purple (PRP) has been developed. Both 3-substituted and 3,3-disubstituted cyclopropenes reacted with PRP, affording the corresponding bis-spirocyclic 3-azabicyclo[3.1.0]hexane cycloadducts in moderate to good yields with high diastereofacial selectivity. Moreover, several unstable 1,2-disubstituted cyclopropenes were successfully trapped by the stable 1,3-dipole under mild conditions. The mechanism of the cycloaddition reactions of cyclopropenes with PRP has been thoroughly studied using density functional theory (DFT) methods at the M11/cc-pVDZ level of theory. The cycloaddition reactions have been found to be HOMOcyclopropene–LUMOylide controlled while the transition-state energies for the reaction of 3-methyl-3-phenylcyclopropene with PRP are fully consistent with the experimentally observed stereoselectivity.https://doi.org/10.3762/bjoc.18.77azomethine ylidescycloadditioncyclopropenesdft calculationsspiro heterocycles |
| spellingShingle | Alexander S. Filatov Olesya V. Khoroshilova Anna G. Larina Vitali M. Boitsov Alexander V. Stepakov Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple Beilstein Journal of Organic Chemistry azomethine ylides cycloaddition cyclopropenes dft calculations spiro heterocycles |
| title | Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple |
| title_full | Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple |
| title_fullStr | Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple |
| title_full_unstemmed | Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple |
| title_short | Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple |
| title_sort | synthesis of bis spirocyclic derivatives of 3 azabicyclo 3 1 0 hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from ruhemann s purple |
| topic | azomethine ylides cycloaddition cyclopropenes dft calculations spiro heterocycles |
| url | https://doi.org/10.3762/bjoc.18.77 |
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