Ligand-enabled Ni-catalysed dicarbofunctionalisation of alkenes with diverse native functional groups
Abstract The transition metal-catalysed dicarbofunctionalisation of unactivated alkenes normally requires exogenous strong coordinated directing groups, thus reducing the overall reaction efficiency. Here, we report a ligand-enabled Ni(II)-catalysed dicarbofunctionalisation of unactivated alkenes wi...
Saved in:
| Main Authors: | , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2024-11-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-54170-9 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1846147568785948672 |
|---|---|
| author | Dao-Ming Wang Hui-Mei Shan Li-Qin She Yu-Qing He Yichen Wu Yong Tang Li-Ping Xu Peng Wang |
| author_facet | Dao-Ming Wang Hui-Mei Shan Li-Qin She Yu-Qing He Yichen Wu Yong Tang Li-Ping Xu Peng Wang |
| author_sort | Dao-Ming Wang |
| collection | DOAJ |
| description | Abstract The transition metal-catalysed dicarbofunctionalisation of unactivated alkenes normally requires exogenous strong coordinated directing groups, thus reducing the overall reaction efficiency. Here, we report a ligand-enabled Ni(II)-catalysed dicarbofunctionalisation of unactivated alkenes with aryl/alkenyl boronic acids and alkyl halides as the coupling partners with a diverse range of native functional groups as the directing group. This dicarbofunctionalisation protocol provides an efficient and direct route towards vicinal 1,2-disubstituted alkanes using primary, secondary, tertiary amides, sulfonamides, as well as secondary and tertiary amines under redox-neutral conditions that are challenging to access through conventional methods. The key to the success of this reaction is the use of a bulky β-diketone ligand, which could enable the insertion of alkene to aryl-Ni(II) species, stabilize the alkyl-Ni(II) species and inhibit the homolytic alkyl-Ni(II) cleavage, supporting by both experimental and computational studies. This dicarbofunctionalisation reaction features the use of native directing group, a broad substrate scope, and excellent scalability. |
| format | Article |
| id | doaj-art-382c7a0fa19c450584ac4d1425b8e2ea |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-382c7a0fa19c450584ac4d1425b8e2ea2024-12-01T12:36:02ZengNature PortfolioNature Communications2041-17232024-11-0115111210.1038/s41467-024-54170-9Ligand-enabled Ni-catalysed dicarbofunctionalisation of alkenes with diverse native functional groupsDao-Ming Wang0Hui-Mei Shan1Li-Qin She2Yu-Qing He3Yichen Wu4Yong Tang5Li-Ping Xu6Peng Wang7State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (CAS)School of Chemistry and Chemical Engineering, Shandong UniversityState Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (CAS)State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (CAS)State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (CAS)State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (CAS)School of Chemistry and Chemical Engineering, Shandong UniversityState Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (CAS)Abstract The transition metal-catalysed dicarbofunctionalisation of unactivated alkenes normally requires exogenous strong coordinated directing groups, thus reducing the overall reaction efficiency. Here, we report a ligand-enabled Ni(II)-catalysed dicarbofunctionalisation of unactivated alkenes with aryl/alkenyl boronic acids and alkyl halides as the coupling partners with a diverse range of native functional groups as the directing group. This dicarbofunctionalisation protocol provides an efficient and direct route towards vicinal 1,2-disubstituted alkanes using primary, secondary, tertiary amides, sulfonamides, as well as secondary and tertiary amines under redox-neutral conditions that are challenging to access through conventional methods. The key to the success of this reaction is the use of a bulky β-diketone ligand, which could enable the insertion of alkene to aryl-Ni(II) species, stabilize the alkyl-Ni(II) species and inhibit the homolytic alkyl-Ni(II) cleavage, supporting by both experimental and computational studies. This dicarbofunctionalisation reaction features the use of native directing group, a broad substrate scope, and excellent scalability.https://doi.org/10.1038/s41467-024-54170-9 |
| spellingShingle | Dao-Ming Wang Hui-Mei Shan Li-Qin She Yu-Qing He Yichen Wu Yong Tang Li-Ping Xu Peng Wang Ligand-enabled Ni-catalysed dicarbofunctionalisation of alkenes with diverse native functional groups Nature Communications |
| title | Ligand-enabled Ni-catalysed dicarbofunctionalisation of alkenes with diverse native functional groups |
| title_full | Ligand-enabled Ni-catalysed dicarbofunctionalisation of alkenes with diverse native functional groups |
| title_fullStr | Ligand-enabled Ni-catalysed dicarbofunctionalisation of alkenes with diverse native functional groups |
| title_full_unstemmed | Ligand-enabled Ni-catalysed dicarbofunctionalisation of alkenes with diverse native functional groups |
| title_short | Ligand-enabled Ni-catalysed dicarbofunctionalisation of alkenes with diverse native functional groups |
| title_sort | ligand enabled ni catalysed dicarbofunctionalisation of alkenes with diverse native functional groups |
| url | https://doi.org/10.1038/s41467-024-54170-9 |
| work_keys_str_mv | AT daomingwang ligandenablednicatalyseddicarbofunctionalisationofalkeneswithdiversenativefunctionalgroups AT huimeishan ligandenablednicatalyseddicarbofunctionalisationofalkeneswithdiversenativefunctionalgroups AT liqinshe ligandenablednicatalyseddicarbofunctionalisationofalkeneswithdiversenativefunctionalgroups AT yuqinghe ligandenablednicatalyseddicarbofunctionalisationofalkeneswithdiversenativefunctionalgroups AT yichenwu ligandenablednicatalyseddicarbofunctionalisationofalkeneswithdiversenativefunctionalgroups AT yongtang ligandenablednicatalyseddicarbofunctionalisationofalkeneswithdiversenativefunctionalgroups AT lipingxu ligandenablednicatalyseddicarbofunctionalisationofalkeneswithdiversenativefunctionalgroups AT pengwang ligandenablednicatalyseddicarbofunctionalisationofalkeneswithdiversenativefunctionalgroups |