Unexpected one-pot formation of the 1H-6a,8a-epiminotricyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study
The unexpected formation of a highly strained polycyclic amine was observed in a one-pot synthesis from cyclopentanone, dimethyl fumarate and ammonium acetate. This multistep reaction includes 1,3-dipolar cycloaddition of dimethyl fumarate to the cyclic azomethine ylide formed in situ from cyclopent...
| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Beilstein-Institut
2019-11-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.15.259 |
| _version_ | 1818719959226777600 |
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| author | Sergey A. Dobrynin Igor A. Kirilyuk Yuri V. Gatilov Andrey A. Kuzhelev Olesya A. Krumkacheva Matvey V. Fedin Michael K. Bowman Elena G. Bagryanskaya |
| author_facet | Sergey A. Dobrynin Igor A. Kirilyuk Yuri V. Gatilov Andrey A. Kuzhelev Olesya A. Krumkacheva Matvey V. Fedin Michael K. Bowman Elena G. Bagryanskaya |
| author_sort | Sergey A. Dobrynin |
| collection | DOAJ |
| description | The unexpected formation of a highly strained polycyclic amine was observed in a one-pot synthesis from cyclopentanone, dimethyl fumarate and ammonium acetate. This multistep reaction includes 1,3-dipolar cycloaddition of dimethyl fumarate to the cyclic azomethine ylide formed in situ from cyclopentanone and ammonia. The polycyclic amine product was easily converted into a sterically shielded polycyclic nitroxide. The EPR spectra and spin relaxation behavior of the nitroxide were studied in solution. The spin relaxation seems well suited for the use as a biological spin label and are comparable with those of cyclic nitroxides with two spirocyclic moieties adjacent to the N–O· group. |
| first_indexed | 2024-12-17T20:15:13Z |
| format | Article |
| id | doaj.art-0a3614a2426f4826a3a078eefb4143ca |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-17T20:15:13Z |
| publishDate | 2019-11-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-0a3614a2426f4826a3a078eefb4143ca2022-12-21T21:34:07ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972019-11-011512664267010.3762/bjoc.15.2591860-5397-15-259Unexpected one-pot formation of the 1H-6a,8a-epiminotricyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR studySergey A. Dobrynin0Igor A. Kirilyuk1Yuri V. Gatilov2Andrey A. Kuzhelev3Olesya A. Krumkacheva4Matvey V. Fedin5Michael K. Bowman6Elena G. Bagryanskaya7N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Lavrentiev Ave. 9, Novosibirsk, 630090, RussiaN. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Lavrentiev Ave. 9, Novosibirsk, 630090, RussiaN. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Lavrentiev Ave. 9, Novosibirsk, 630090, RussiaN. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Lavrentiev Ave. 9, Novosibirsk, 630090, RussiaNovosibirsk State University, Pirogova Str. 2, Novosibirsk, 630090, RussiaNovosibirsk State University, Pirogova Str. 2, Novosibirsk, 630090, RussiaN. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Lavrentiev Ave. 9, Novosibirsk, 630090, RussiaN. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Lavrentiev Ave. 9, Novosibirsk, 630090, RussiaThe unexpected formation of a highly strained polycyclic amine was observed in a one-pot synthesis from cyclopentanone, dimethyl fumarate and ammonium acetate. This multistep reaction includes 1,3-dipolar cycloaddition of dimethyl fumarate to the cyclic azomethine ylide formed in situ from cyclopentanone and ammonia. The polycyclic amine product was easily converted into a sterically shielded polycyclic nitroxide. The EPR spectra and spin relaxation behavior of the nitroxide were studied in solution. The spin relaxation seems well suited for the use as a biological spin label and are comparable with those of cyclic nitroxides with two spirocyclic moieties adjacent to the N–O· group.https://doi.org/10.3762/bjoc.15.259domino reactionseprnitroxidespin relaxation |
| spellingShingle | Sergey A. Dobrynin Igor A. Kirilyuk Yuri V. Gatilov Andrey A. Kuzhelev Olesya A. Krumkacheva Matvey V. Fedin Michael K. Bowman Elena G. Bagryanskaya Unexpected one-pot formation of the 1H-6a,8a-epiminotricyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study Beilstein Journal of Organic Chemistry domino reactions epr nitroxide spin relaxation |
| title | Unexpected one-pot formation of the 1H-6a,8a-epiminotricyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study |
| title_full | Unexpected one-pot formation of the 1H-6a,8a-epiminotricyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study |
| title_fullStr | Unexpected one-pot formation of the 1H-6a,8a-epiminotricyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study |
| title_full_unstemmed | Unexpected one-pot formation of the 1H-6a,8a-epiminotricyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study |
| title_short | Unexpected one-pot formation of the 1H-6a,8a-epiminotricyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study |
| title_sort | unexpected one pot formation of the 1h 6a 8a epiminotricyclopenta a c e 8 annulene system from cyclopentanone ammonia and dimethyl fumarate synthesis of highly strained polycyclic nitroxide and epr study |
| topic | domino reactions epr nitroxide spin relaxation |
| url | https://doi.org/10.3762/bjoc.15.259 |
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