Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks
Abstract The past century has witnessed a large number of reports on the Z/E isomerization of alkenes. However, the vast majority of them are still limited to the isomerization of di- and tri-substituted alkenes. The stereospecific Z/E isomerization of tetrasubstituted alkenes remains to be an under...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-04-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-47404-3 |
| _version_ | 1827277058008416256 |
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| author | Jie Wang Jun Gu Jia-Yu Zou Meng-Jie Zhang Rui Shen Zhiwen Ye Ping-Xun Xu Ying He |
| author_facet | Jie Wang Jun Gu Jia-Yu Zou Meng-Jie Zhang Rui Shen Zhiwen Ye Ping-Xun Xu Ying He |
| author_sort | Jie Wang |
| collection | DOAJ |
| description | Abstract The past century has witnessed a large number of reports on the Z/E isomerization of alkenes. However, the vast majority of them are still limited to the isomerization of di- and tri-substituted alkenes. The stereospecific Z/E isomerization of tetrasubstituted alkenes remains to be an underdeveloped area, thus lacking in a stereodivergent synthesis of axially chiral alkenes. Herein we report the atroposelective synthesis of tetrasubstituted alkene analogues by asymmetric allylic substitution-isomerization, followed by their Z/E isomerization via triplet energy transfer photocatalysis. In this regard, the stereodivergent synthesis of axially chiral N-vinylquinolinones is achieved efficiently. Mechanistic studies indicate that the benzylic radical generation and distribution are two key factors for preserving the enantioselectivities of axially chiral compounds. |
| first_indexed | 2024-04-24T07:14:31Z |
| format | Article |
| id | doaj.art-cf9500e55ce848e3838d328feb0e8844 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-04-24T07:14:31Z |
| publishDate | 2024-04-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-cf9500e55ce848e3838d328feb0e88442024-04-21T11:24:30ZengNature PortfolioNature Communications2041-17232024-04-011511810.1038/s41467-024-47404-3Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworksJie Wang0Jun Gu1Jia-Yu Zou2Meng-Jie Zhang3Rui Shen4Zhiwen Ye5Ping-Xun Xu6Ying He7School of Chemistry and Chemical Engineering, Nanjing University of Science and TechnologySchool of Chemistry and Chemical Engineering, Nanjing University of Science and TechnologySchool of Chemistry and Chemical Engineering, Nanjing University of Science and TechnologySchool of Chemistry and Chemical Engineering, Nanjing University of Science and TechnologySchool of Chemistry and Chemical Engineering, Nanjing University of Science and TechnologySchool of Chemistry and Chemical Engineering, Nanjing University of Science and TechnologySchool of Chemistry and Chemical Engineering, Nanjing University of Science and TechnologySchool of Chemistry and Chemical Engineering, Nanjing University of Science and TechnologyAbstract The past century has witnessed a large number of reports on the Z/E isomerization of alkenes. However, the vast majority of them are still limited to the isomerization of di- and tri-substituted alkenes. The stereospecific Z/E isomerization of tetrasubstituted alkenes remains to be an underdeveloped area, thus lacking in a stereodivergent synthesis of axially chiral alkenes. Herein we report the atroposelective synthesis of tetrasubstituted alkene analogues by asymmetric allylic substitution-isomerization, followed by their Z/E isomerization via triplet energy transfer photocatalysis. In this regard, the stereodivergent synthesis of axially chiral N-vinylquinolinones is achieved efficiently. Mechanistic studies indicate that the benzylic radical generation and distribution are two key factors for preserving the enantioselectivities of axially chiral compounds.https://doi.org/10.1038/s41467-024-47404-3 |
| spellingShingle | Jie Wang Jun Gu Jia-Yu Zou Meng-Jie Zhang Rui Shen Zhiwen Ye Ping-Xun Xu Ying He Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks Nature Communications |
| title | Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks |
| title_full | Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks |
| title_fullStr | Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks |
| title_full_unstemmed | Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks |
| title_short | Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks |
| title_sort | photocatalytic z e isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks |
| url | https://doi.org/10.1038/s41467-024-47404-3 |
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