Tailored chiral phosphoramidites support highly enantioselective Pd catalysts for asymmetric aminoalkylative amination
Abstract Even though tuning electronic effect of chiral ligands has proven to be a promising method for designing efficient catalysts, the potential to achieve highly selective reactions by this strategy remains largely unexplored. Here, we report a palladium-catalyzed enantioselective ring-closing...
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Nature Portfolio
2024-12-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-54328-5 |
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| author | Suchen Zou Zeyu Zhao Guoqing Yang Hanmin Huang |
| author_facet | Suchen Zou Zeyu Zhao Guoqing Yang Hanmin Huang |
| author_sort | Suchen Zou |
| collection | DOAJ |
| description | Abstract Even though tuning electronic effect of chiral ligands has proven to be a promising method for designing efficient catalysts, the potential to achieve highly selective reactions by this strategy remains largely unexplored. Here, we report a palladium-catalyzed enantioselective ring-closing aminoalkylative amination of aminoenynes enabled by rationally tuning the remote electronic property of 1,1’-binaphthol-derived phosphoramidites. With a tailored 6,6’-CN-substituted 1,1’-binaphthol-derived phosphoramidite as a ligand, a broad range of aromatic amines are compatible with this reaction, allowing the efficient synthesis of a series of enantioenriched exocyclic allenylamines bearing saturated N-heterocycles with up to >99% enantiomeric excess. Remarkably, a one-pot aminoalkylative amination/hydroamination process for the rapid synthesis of chiral spirodiamines promoted by this catalytic system is also established. Detailed mechanistic studies provide solid evidence to support that the remote electronic character of these chiral ligands can efficiently tuning the enantioselectivity by altering the length of the allylic C-Pd bond of the key catalytic intermediate. |
| format | Article |
| id | doaj-art-949df99f102c4ef8a3559cfdbffed44a |
| institution | OA Journals |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-949df99f102c4ef8a3559cfdbffed44a2025-08-20T02:20:48ZengNature PortfolioNature Communications2041-17232024-12-0115111110.1038/s41467-024-54328-5Tailored chiral phosphoramidites support highly enantioselective Pd catalysts for asymmetric aminoalkylative aminationSuchen Zou0Zeyu Zhao1Guoqing Yang2Hanmin Huang3Key Laboratory of Precision and Intelligent Chemistry and Department of Chemistry, University of Science and Technology of ChinaKey Laboratory of Precision and Intelligent Chemistry and Department of Chemistry, University of Science and Technology of ChinaKey Laboratory of Precision and Intelligent Chemistry and Department of Chemistry, University of Science and Technology of ChinaKey Laboratory of Precision and Intelligent Chemistry and Department of Chemistry, University of Science and Technology of ChinaAbstract Even though tuning electronic effect of chiral ligands has proven to be a promising method for designing efficient catalysts, the potential to achieve highly selective reactions by this strategy remains largely unexplored. Here, we report a palladium-catalyzed enantioselective ring-closing aminoalkylative amination of aminoenynes enabled by rationally tuning the remote electronic property of 1,1’-binaphthol-derived phosphoramidites. With a tailored 6,6’-CN-substituted 1,1’-binaphthol-derived phosphoramidite as a ligand, a broad range of aromatic amines are compatible with this reaction, allowing the efficient synthesis of a series of enantioenriched exocyclic allenylamines bearing saturated N-heterocycles with up to >99% enantiomeric excess. Remarkably, a one-pot aminoalkylative amination/hydroamination process for the rapid synthesis of chiral spirodiamines promoted by this catalytic system is also established. Detailed mechanistic studies provide solid evidence to support that the remote electronic character of these chiral ligands can efficiently tuning the enantioselectivity by altering the length of the allylic C-Pd bond of the key catalytic intermediate.https://doi.org/10.1038/s41467-024-54328-5 |
| spellingShingle | Suchen Zou Zeyu Zhao Guoqing Yang Hanmin Huang Tailored chiral phosphoramidites support highly enantioselective Pd catalysts for asymmetric aminoalkylative amination Nature Communications |
| title | Tailored chiral phosphoramidites support highly enantioselective Pd catalysts for asymmetric aminoalkylative amination |
| title_full | Tailored chiral phosphoramidites support highly enantioselective Pd catalysts for asymmetric aminoalkylative amination |
| title_fullStr | Tailored chiral phosphoramidites support highly enantioselective Pd catalysts for asymmetric aminoalkylative amination |
| title_full_unstemmed | Tailored chiral phosphoramidites support highly enantioselective Pd catalysts for asymmetric aminoalkylative amination |
| title_short | Tailored chiral phosphoramidites support highly enantioselective Pd catalysts for asymmetric aminoalkylative amination |
| title_sort | tailored chiral phosphoramidites support highly enantioselective pd catalysts for asymmetric aminoalkylative amination |
| url | https://doi.org/10.1038/s41467-024-54328-5 |
| work_keys_str_mv | AT suchenzou tailoredchiralphosphoramiditessupporthighlyenantioselectivepdcatalystsforasymmetricaminoalkylativeamination AT zeyuzhao tailoredchiralphosphoramiditessupporthighlyenantioselectivepdcatalystsforasymmetricaminoalkylativeamination AT guoqingyang tailoredchiralphosphoramiditessupporthighlyenantioselectivepdcatalystsforasymmetricaminoalkylativeamination AT hanminhuang tailoredchiralphosphoramiditessupporthighlyenantioselectivepdcatalystsforasymmetricaminoalkylativeamination |