Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis
Abstract We herein describe an asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes with 1,3-enynes. A synergistic chiral primary amine/Pd catalyst was identified to facilitate the utilization of 1,3-enynes as atom-economic and achiral allene precursors. The synergistic catalysis enabl...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-05-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-38488-4 |
| _version_ | 1797817888551206912 |
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| author | Chang You Mingying Shi Xueling Mi Sanzhong Luo |
| author_facet | Chang You Mingying Shi Xueling Mi Sanzhong Luo |
| author_sort | Chang You |
| collection | DOAJ |
| description | Abstract We herein describe an asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes with 1,3-enynes. A synergistic chiral primary amine/Pd catalyst was identified to facilitate the utilization of 1,3-enynes as atom-economic and achiral allene precursors. The synergistic catalysis enables the construction of all-carbon quaternary centers-tethered allenes bearing non-adjacent 1,3-axial central stereogenic centers in high level of diastereo- and enantio-selectivity. By switching the configurations of ligands and aminocatalysts, diastereodivergence can be achieved and any of the four diastereoisomers can be accessed in high diastereo- and enantio- selectivity. |
| first_indexed | 2024-03-13T09:00:08Z |
| format | Article |
| id | doaj.art-120d95e28ff64e22bb479ff122ace60b |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-13T09:00:08Z |
| publishDate | 2023-05-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-120d95e28ff64e22bb479ff122ace60b2023-05-28T11:20:58ZengNature PortfolioNature Communications2041-17232023-05-011411710.1038/s41467-023-38488-4Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysisChang You0Mingying Shi1Xueling Mi2Sanzhong Luo3Center of Basic Molecular Science, Department of Chemistry, Tsinghua UniversityCollege of Chemistry, Beijing Normal UniversityCollege of Chemistry, Beijing Normal UniversityCenter of Basic Molecular Science, Department of Chemistry, Tsinghua UniversityAbstract We herein describe an asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes with 1,3-enynes. A synergistic chiral primary amine/Pd catalyst was identified to facilitate the utilization of 1,3-enynes as atom-economic and achiral allene precursors. The synergistic catalysis enables the construction of all-carbon quaternary centers-tethered allenes bearing non-adjacent 1,3-axial central stereogenic centers in high level of diastereo- and enantio-selectivity. By switching the configurations of ligands and aminocatalysts, diastereodivergence can be achieved and any of the four diastereoisomers can be accessed in high diastereo- and enantio- selectivity.https://doi.org/10.1038/s41467-023-38488-4 |
| spellingShingle | Chang You Mingying Shi Xueling Mi Sanzhong Luo Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis Nature Communications |
| title | Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis |
| title_full | Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis |
| title_fullStr | Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis |
| title_full_unstemmed | Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis |
| title_short | Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis |
| title_sort | asymmetric α allylic allenylation of β ketocarbonyls and aldehydes by synergistic pd chiral primary amine catalysis |
| url | https://doi.org/10.1038/s41467-023-38488-4 |
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