9a-Phenyl-2,3,3a,3b,9a,9b-hexahydro-4<i>H</i>-furo[3‘,2’:3,4]cyclobuta- [1,2-b]chromen-4-one: A Flavone-Based [2 + 2]-Photocycloadduct
The intermolecular [2 + 2]-photocycloaddition of the parent flavone molecule (<b>4</b>) as the triplet energy-accepting species and the electron-rich alkene 2, 3-dihydrofuran (<b>5</b>) was performed by visible-light-mediated triplet-sensitization with an iridium-based organo...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-07-01
|
| Series: | Molbank |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1422-8599/2021/3/M1256 |
| _version_ | 1797518000001122304 |
|---|---|
| author | Jens Lefarth Jörg Neudörfl Axel G. Griesbeck |
| author_facet | Jens Lefarth Jörg Neudörfl Axel G. Griesbeck |
| author_sort | Jens Lefarth |
| collection | DOAJ |
| description | The intermolecular [2 + 2]-photocycloaddition of the parent flavone molecule (<b>4</b>) as the triplet energy-accepting species and the electron-rich alkene 2, 3-dihydrofuran (<b>5</b>) was performed by visible-light-mediated triplet-sensitization with an iridium-based organometallic sensitizer. The reaction proceeds with high diastereo- and regioselectivity (>98:2 for the regiochemical orientation and with 95% d.s.). In contrast to numerous other ene/enone combinations that are described in the literature and were also performed by us, the reaction between <b>4</b> and <b>5</b> almost solely afforded the <i>cis</i>-<i>syn</i>-<i>cis</i> cyclobutane <b>6,</b> whereas analogous conjugated six- and five-membered cycloalkenones preferentially react to <i>cis</i>-<i>anti</i>-<i>cis</i> cyclobutanes or a mixture of both diastereoisomers (e.g., for the cyclohexanone-derived example <b>9</b>). |
| first_indexed | 2024-03-10T07:24:01Z |
| format | Article |
| id | doaj.art-46a1196d5ae8403cba39a0f1b0512e7a |
| institution | Directory Open Access Journal |
| issn | 1422-8599 |
| language | English |
| last_indexed | 2024-03-10T07:24:01Z |
| publishDate | 2021-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molbank |
| spelling | doaj.art-46a1196d5ae8403cba39a0f1b0512e7a2023-11-22T14:22:33ZengMDPI AGMolbank1422-85992021-07-0120213M125610.3390/M12569a-Phenyl-2,3,3a,3b,9a,9b-hexahydro-4<i>H</i>-furo[3‘,2’:3,4]cyclobuta- [1,2-b]chromen-4-one: A Flavone-Based [2 + 2]-PhotocycloadductJens Lefarth0Jörg Neudörfl1Axel G. Griesbeck2Department of Chemistry, Faculty of Natural Sciences and Mathematics, University of Cologne, Greinstr. 4, 50939 Köln, GermanyDepartment of Chemistry, Faculty of Natural Sciences and Mathematics, University of Cologne, Greinstr. 4, 50939 Köln, GermanyDepartment of Chemistry, Faculty of Natural Sciences and Mathematics, University of Cologne, Greinstr. 4, 50939 Köln, GermanyThe intermolecular [2 + 2]-photocycloaddition of the parent flavone molecule (<b>4</b>) as the triplet energy-accepting species and the electron-rich alkene 2, 3-dihydrofuran (<b>5</b>) was performed by visible-light-mediated triplet-sensitization with an iridium-based organometallic sensitizer. The reaction proceeds with high diastereo- and regioselectivity (>98:2 for the regiochemical orientation and with 95% d.s.). In contrast to numerous other ene/enone combinations that are described in the literature and were also performed by us, the reaction between <b>4</b> and <b>5</b> almost solely afforded the <i>cis</i>-<i>syn</i>-<i>cis</i> cyclobutane <b>6,</b> whereas analogous conjugated six- and five-membered cycloalkenones preferentially react to <i>cis</i>-<i>anti</i>-<i>cis</i> cyclobutanes or a mixture of both diastereoisomers (e.g., for the cyclohexanone-derived example <b>9</b>).https://www.mdpi.com/1422-8599/2021/3/M1256photocatalysisflavone[2 + 2]-photocycloadditionstereoselectivity |
| spellingShingle | Jens Lefarth Jörg Neudörfl Axel G. Griesbeck 9a-Phenyl-2,3,3a,3b,9a,9b-hexahydro-4<i>H</i>-furo[3‘,2’:3,4]cyclobuta- [1,2-b]chromen-4-one: A Flavone-Based [2 + 2]-Photocycloadduct Molbank photocatalysis flavone [2 + 2]-photocycloaddition stereoselectivity |
| title | 9a-Phenyl-2,3,3a,3b,9a,9b-hexahydro-4<i>H</i>-furo[3‘,2’:3,4]cyclobuta- [1,2-b]chromen-4-one: A Flavone-Based [2 + 2]-Photocycloadduct |
| title_full | 9a-Phenyl-2,3,3a,3b,9a,9b-hexahydro-4<i>H</i>-furo[3‘,2’:3,4]cyclobuta- [1,2-b]chromen-4-one: A Flavone-Based [2 + 2]-Photocycloadduct |
| title_fullStr | 9a-Phenyl-2,3,3a,3b,9a,9b-hexahydro-4<i>H</i>-furo[3‘,2’:3,4]cyclobuta- [1,2-b]chromen-4-one: A Flavone-Based [2 + 2]-Photocycloadduct |
| title_full_unstemmed | 9a-Phenyl-2,3,3a,3b,9a,9b-hexahydro-4<i>H</i>-furo[3‘,2’:3,4]cyclobuta- [1,2-b]chromen-4-one: A Flavone-Based [2 + 2]-Photocycloadduct |
| title_short | 9a-Phenyl-2,3,3a,3b,9a,9b-hexahydro-4<i>H</i>-furo[3‘,2’:3,4]cyclobuta- [1,2-b]chromen-4-one: A Flavone-Based [2 + 2]-Photocycloadduct |
| title_sort | 9a phenyl 2 3 3a 3b 9a 9b hexahydro 4 i h i furo 3 2 3 4 cyclobuta 1 2 b chromen 4 one a flavone based 2 2 photocycloadduct |
| topic | photocatalysis flavone [2 + 2]-photocycloaddition stereoselectivity |
| url | https://www.mdpi.com/1422-8599/2021/3/M1256 |
| work_keys_str_mv | AT jenslefarth 9aphenyl233a3b9a9bhexahydro4ihifuro3234cyclobuta12bchromen4oneaflavonebased22photocycloadduct AT jorgneudorfl 9aphenyl233a3b9a9bhexahydro4ihifuro3234cyclobuta12bchromen4oneaflavonebased22photocycloadduct AT axelggriesbeck 9aphenyl233a3b9a9bhexahydro4ihifuro3234cyclobuta12bchromen4oneaflavonebased22photocycloadduct |