Asymmetric S=N-embedded polyaromatic construction via enantioselective Pd-catalyzed C–H activation
Abstract Heteroatom-doped polyaromatic hydrocarbons show great potential for advancing photoelectric materials. SVI=N doping, characterized by soft-hard atom binding, donor-acceptor transmission, and chiroptical tuning, provides a powerful approach for further optimizing the performance and function...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-03-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-57251-5 |
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| author | Daming Zeng Xinyu Zhang Ming Wang Xuefeng Jiang |
| author_facet | Daming Zeng Xinyu Zhang Ming Wang Xuefeng Jiang |
| author_sort | Daming Zeng |
| collection | DOAJ |
| description | Abstract Heteroatom-doped polyaromatic hydrocarbons show great potential for advancing photoelectric materials. SVI=N doping, characterized by soft-hard atom binding, donor-acceptor transmission, and chiroptical tuning, provides a powerful approach for further optimizing the performance and functionality of these materials. However, the introduction of chiral sulfur(VI) has been a formidable challenge due to the intricate enantioselective discrimination and embedded linkages with the heteroatoms in the polyaromatic systems. Herein, we establish an enantioselective Pd-catalyzed desymmetrization of diaryl sulfoximines and sulfondiimines to access the chiral SVI=N-doped heterocycles with high yields and enantioselectivities. The flexibility and rigidity of the molecule has a distinct effect on the enantioselectivity. The split aromatic compounds exhibit C–H···π interactions involving the additive TMCPA with the ligand and the S-aryl motif, producing the (R)-configuration, while combined aromatic compounds exhibit the opposite (S)-configuration due to the restricted bond rotation. The photophysical and chiroptical study demonstrates an SVI=N-doped carbazole-based polyaromatic heterocycle with intense double absorption peaks and a favorable luminescence dissymmetry factor. |
| format | Article |
| id | doaj-art-a79d588827f94fdaa4ee2e3fb4a1dbd8 |
| institution | OA Journals |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-a79d588827f94fdaa4ee2e3fb4a1dbd82025-08-20T02:10:10ZengNature PortfolioNature Communications2041-17232025-03-0116111010.1038/s41467-025-57251-5Asymmetric S=N-embedded polyaromatic construction via enantioselective Pd-catalyzed C–H activationDaming Zeng0Xinyu Zhang1Ming Wang2Xuefeng Jiang3Hainan Institute of East China Normal University, East China Normal UniversityHainan Institute of East China Normal University, East China Normal UniversityHainan Institute of East China Normal University, East China Normal UniversityHainan Institute of East China Normal University, East China Normal UniversityAbstract Heteroatom-doped polyaromatic hydrocarbons show great potential for advancing photoelectric materials. SVI=N doping, characterized by soft-hard atom binding, donor-acceptor transmission, and chiroptical tuning, provides a powerful approach for further optimizing the performance and functionality of these materials. However, the introduction of chiral sulfur(VI) has been a formidable challenge due to the intricate enantioselective discrimination and embedded linkages with the heteroatoms in the polyaromatic systems. Herein, we establish an enantioselective Pd-catalyzed desymmetrization of diaryl sulfoximines and sulfondiimines to access the chiral SVI=N-doped heterocycles with high yields and enantioselectivities. The flexibility and rigidity of the molecule has a distinct effect on the enantioselectivity. The split aromatic compounds exhibit C–H···π interactions involving the additive TMCPA with the ligand and the S-aryl motif, producing the (R)-configuration, while combined aromatic compounds exhibit the opposite (S)-configuration due to the restricted bond rotation. The photophysical and chiroptical study demonstrates an SVI=N-doped carbazole-based polyaromatic heterocycle with intense double absorption peaks and a favorable luminescence dissymmetry factor.https://doi.org/10.1038/s41467-025-57251-5 |
| spellingShingle | Daming Zeng Xinyu Zhang Ming Wang Xuefeng Jiang Asymmetric S=N-embedded polyaromatic construction via enantioselective Pd-catalyzed C–H activation Nature Communications |
| title | Asymmetric S=N-embedded polyaromatic construction via enantioselective Pd-catalyzed C–H activation |
| title_full | Asymmetric S=N-embedded polyaromatic construction via enantioselective Pd-catalyzed C–H activation |
| title_fullStr | Asymmetric S=N-embedded polyaromatic construction via enantioselective Pd-catalyzed C–H activation |
| title_full_unstemmed | Asymmetric S=N-embedded polyaromatic construction via enantioselective Pd-catalyzed C–H activation |
| title_short | Asymmetric S=N-embedded polyaromatic construction via enantioselective Pd-catalyzed C–H activation |
| title_sort | asymmetric s n embedded polyaromatic construction via enantioselective pd catalyzed c h activation |
| url | https://doi.org/10.1038/s41467-025-57251-5 |
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