Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution
Abstract Metal-centered chirality has been recognized for over one century, and stereogenic-at-metal complexes where chirality is exclusively attributed to the metal center due to the specific coordination pattern of achiral ligands around the metal ion, has been broadly utilized in diverse areas of...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-55341-4 |
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| author | Yun-Peng Chu Xue-Lin Yue De-Hai Liu Chuanyong Wang Jiajia Ma |
| author_facet | Yun-Peng Chu Xue-Lin Yue De-Hai Liu Chuanyong Wang Jiajia Ma |
| author_sort | Yun-Peng Chu |
| collection | DOAJ |
| description | Abstract Metal-centered chirality has been recognized for over one century, and stereogenic-at-metal complexes where chirality is exclusively attributed to the metal center due to the specific coordination pattern of achiral ligands around the metal ion, has been broadly utilized in diverse areas of natural science. However, synthesis of these molecules remains constrained. Notably, while asymmetric catalysis has played a crucial role in the production of optically active organic molecules, its application to stereogenic-at-metal complexes is less straightforward. In this study, we introduce a kinetic resolution strategy employing a Pd-catalyzed asymmetric Suzuki-Miyaura cross-coupling reaction that efficiently produces optically active stereogenic-at-iridium complexes from racemic mixtures with high selectivity (achieving an s-factor of up to 133). This method enables further synthesis of complexes relevant to chiral metallodrugs and photosensitizers, underscoring the practical utility of our approach. Mechanistic studies suggest that reductive elimination is likely the turnover-limiting step over the Suzuki-Miyaura cross-coupling. |
| format | Article |
| id | doaj-art-a4b64751dfa943f08cc829a2fa946b35 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-a4b64751dfa943f08cc829a2fa946b352025-02-02T12:33:37ZengNature PortfolioNature Communications2041-17232025-01-0116111010.1038/s41467-024-55341-4Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolutionYun-Peng Chu0Xue-Lin Yue1De-Hai Liu2Chuanyong Wang3Jiajia Ma4Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong UniversityFrontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong UniversityFrontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong UniversityCollege of Chemistry and Chemical Engineering, Yangzhou UniversityFrontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong UniversityAbstract Metal-centered chirality has been recognized for over one century, and stereogenic-at-metal complexes where chirality is exclusively attributed to the metal center due to the specific coordination pattern of achiral ligands around the metal ion, has been broadly utilized in diverse areas of natural science. However, synthesis of these molecules remains constrained. Notably, while asymmetric catalysis has played a crucial role in the production of optically active organic molecules, its application to stereogenic-at-metal complexes is less straightforward. In this study, we introduce a kinetic resolution strategy employing a Pd-catalyzed asymmetric Suzuki-Miyaura cross-coupling reaction that efficiently produces optically active stereogenic-at-iridium complexes from racemic mixtures with high selectivity (achieving an s-factor of up to 133). This method enables further synthesis of complexes relevant to chiral metallodrugs and photosensitizers, underscoring the practical utility of our approach. Mechanistic studies suggest that reductive elimination is likely the turnover-limiting step over the Suzuki-Miyaura cross-coupling.https://doi.org/10.1038/s41467-024-55341-4 |
| spellingShingle | Yun-Peng Chu Xue-Lin Yue De-Hai Liu Chuanyong Wang Jiajia Ma Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution Nature Communications |
| title | Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution |
| title_full | Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution |
| title_fullStr | Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution |
| title_full_unstemmed | Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution |
| title_short | Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution |
| title_sort | asymmetric synthesis of stereogenic at iridium iii complexes through pd catalyzed kinetic resolution |
| url | https://doi.org/10.1038/s41467-024-55341-4 |
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