Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands
Abstract A wide range of Cu(II)-catalyzed C–H activation reactions have been realized since 2006, however, whether a C–H metalation mechanism similar to Pd(II)-catalyzed C–H activation reaction is operating remains an open question. To address this question and ultimately develop ligand accelerated...
| Main Authors: | , , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-11-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-43278-z |
| _version_ | 1797452084083163136 |
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| author | Xin Kuang Jian-Jun Li Tao Liu Chang-Hua Ding Kevin Wu Peng Wang Jin-Quan Yu |
| author_facet | Xin Kuang Jian-Jun Li Tao Liu Chang-Hua Ding Kevin Wu Peng Wang Jin-Quan Yu |
| author_sort | Xin Kuang |
| collection | DOAJ |
| description | Abstract A wide range of Cu(II)-catalyzed C–H activation reactions have been realized since 2006, however, whether a C–H metalation mechanism similar to Pd(II)-catalyzed C–H activation reaction is operating remains an open question. To address this question and ultimately develop ligand accelerated Cu(II)-catalyzed C–H activation reactions, realizing the enantioselective version and investigating the mechanism is critically important. With a modified chiral BINOL ligand, we report the first example of Cu-mediated enantioselective C–H activation reaction for the construction of planar chiral ferrocenes with high yields and stereoinduction. The key to the success of this reaction is the discovery of a ligand acceleration effect with the BINOL-based diol ligand in the directed Cu-catalyzed C–H alkynylation of ferrocene derivatives bearing an oxazoline-aniline directing group. This transformation is compatible with terminal aryl and alkyl alkynes, which are incompatible with Pd-catalyzed C–H activation reactions. This finding provides an invaluable mechanistic information in determining whether Cu(II) cleaves C–H bonds via CMD pathway in analogous manner to Pd(II) catalysts. |
| first_indexed | 2024-03-09T15:03:39Z |
| format | Article |
| id | doaj.art-16bb4d1fbd294edbbe6d27e2c09628e7 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-09T15:03:39Z |
| publishDate | 2023-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-16bb4d1fbd294edbbe6d27e2c09628e72023-11-26T13:46:17ZengNature PortfolioNature Communications2041-17232023-11-0114111010.1038/s41467-023-43278-zCu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligandsXin Kuang0Jian-Jun Li1Tao Liu2Chang-Hua Ding3Kevin Wu4Peng Wang5Jin-Quan Yu6State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic ChemistryState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic ChemistryState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic ChemistrySchool of Science, Shanghai UniversityThe Scripps Research Institute (TSRI)State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic ChemistryThe Scripps Research Institute (TSRI)Abstract A wide range of Cu(II)-catalyzed C–H activation reactions have been realized since 2006, however, whether a C–H metalation mechanism similar to Pd(II)-catalyzed C–H activation reaction is operating remains an open question. To address this question and ultimately develop ligand accelerated Cu(II)-catalyzed C–H activation reactions, realizing the enantioselective version and investigating the mechanism is critically important. With a modified chiral BINOL ligand, we report the first example of Cu-mediated enantioselective C–H activation reaction for the construction of planar chiral ferrocenes with high yields and stereoinduction. The key to the success of this reaction is the discovery of a ligand acceleration effect with the BINOL-based diol ligand in the directed Cu-catalyzed C–H alkynylation of ferrocene derivatives bearing an oxazoline-aniline directing group. This transformation is compatible with terminal aryl and alkyl alkynes, which are incompatible with Pd-catalyzed C–H activation reactions. This finding provides an invaluable mechanistic information in determining whether Cu(II) cleaves C–H bonds via CMD pathway in analogous manner to Pd(II) catalysts.https://doi.org/10.1038/s41467-023-43278-z |
| spellingShingle | Xin Kuang Jian-Jun Li Tao Liu Chang-Hua Ding Kevin Wu Peng Wang Jin-Quan Yu Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands Nature Communications |
| title | Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands |
| title_full | Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands |
| title_fullStr | Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands |
| title_full_unstemmed | Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands |
| title_short | Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands |
| title_sort | cu mediated enantioselective c h alkynylation of ferrocenes with chiral binol ligands |
| url | https://doi.org/10.1038/s41467-023-43278-z |
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