Ligand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halides
Abstract α-Tertiary aliphatic amides are key elements in organic molecules, which are abundantly present in natural products, pharmaceuticals, agrochemicals, and functional organic materials. Enantioconvergent alkyl-alkyl bond-forming process is one of the most straightforward and efficient, yet hig...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2023-05-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-38702-3 |
| _version_ | 1797817908391313408 |
|---|---|
| author | Wen-Tao Zhao Jian-Xin Zhang Bi-Hong Chen Wei Shu |
| author_facet | Wen-Tao Zhao Jian-Xin Zhang Bi-Hong Chen Wei Shu |
| author_sort | Wen-Tao Zhao |
| collection | DOAJ |
| description | Abstract α-Tertiary aliphatic amides are key elements in organic molecules, which are abundantly present in natural products, pharmaceuticals, agrochemicals, and functional organic materials. Enantioconvergent alkyl-alkyl bond-forming process is one of the most straightforward and efficient, yet highly challenging ways to build such stereogenic carbon centers. Herein, we report an enantioselective alkyl-alkyl cross-coupling between two different alkyl electrophiles to access α-tertiary aliphatic amides. With a newly-developed chiral tridentate ligand, two distinct alkyl halides were successfully cross-coupled together to forge an alkyl-alkyl bond enantioselectively under reductive conditions. Mechanistic investigations reveal that one alkyl halides exclusively undergo oxidative addition with nickel versus in-situ formation of alkyl zinc reagents from the other alkyl halides, rendering formal reductive alkyl-alkyl cross-coupling from easily available alkyl electrophiles without preformation of organometallic reagents. |
| first_indexed | 2024-03-13T09:00:25Z |
| format | Article |
| id | doaj.art-565feecdcf754707831f103b38efd494 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-13T09:00:25Z |
| publishDate | 2023-05-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-565feecdcf754707831f103b38efd4942023-05-28T11:21:37ZengNature PortfolioNature Communications2041-17232023-05-011411710.1038/s41467-023-38702-3Ligand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halidesWen-Tao Zhao0Jian-Xin Zhang1Bi-Hong Chen2Wei Shu3Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and TechnologyShenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and TechnologyShenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and TechnologyShenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and TechnologyAbstract α-Tertiary aliphatic amides are key elements in organic molecules, which are abundantly present in natural products, pharmaceuticals, agrochemicals, and functional organic materials. Enantioconvergent alkyl-alkyl bond-forming process is one of the most straightforward and efficient, yet highly challenging ways to build such stereogenic carbon centers. Herein, we report an enantioselective alkyl-alkyl cross-coupling between two different alkyl electrophiles to access α-tertiary aliphatic amides. With a newly-developed chiral tridentate ligand, two distinct alkyl halides were successfully cross-coupled together to forge an alkyl-alkyl bond enantioselectively under reductive conditions. Mechanistic investigations reveal that one alkyl halides exclusively undergo oxidative addition with nickel versus in-situ formation of alkyl zinc reagents from the other alkyl halides, rendering formal reductive alkyl-alkyl cross-coupling from easily available alkyl electrophiles without preformation of organometallic reagents.https://doi.org/10.1038/s41467-023-38702-3 |
| spellingShingle | Wen-Tao Zhao Jian-Xin Zhang Bi-Hong Chen Wei Shu Ligand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halides Nature Communications |
| title | Ligand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halides |
| title_full | Ligand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halides |
| title_fullStr | Ligand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halides |
| title_full_unstemmed | Ligand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halides |
| title_short | Ligand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halides |
| title_sort | ligand enabled ni catalysed enantioconvergent intermolecular alkyl alkyl cross coupling between distinct alkyl halides |
| url | https://doi.org/10.1038/s41467-023-38702-3 |
| work_keys_str_mv | AT wentaozhao ligandenablednicatalysedenantioconvergentintermolecularalkylalkylcrosscouplingbetweendistinctalkylhalides AT jianxinzhang ligandenablednicatalysedenantioconvergentintermolecularalkylalkylcrosscouplingbetweendistinctalkylhalides AT bihongchen ligandenablednicatalysedenantioconvergentintermolecularalkylalkylcrosscouplingbetweendistinctalkylhalides AT weishu ligandenablednicatalysedenantioconvergentintermolecularalkylalkylcrosscouplingbetweendistinctalkylhalides |