A Palladium Complex as an Asymmetric π-Lewis Base Catalyst for Activating 1,3-Dienes
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| Titel: | A Palladium Complex as an Asymmetric π-Lewis Base Catalyst for Activating 1,3-Dienes |
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| Autoren: | Qin Ouyang, Xin-Yue Gao, Ben-Xian Xiao, Ke Xie, Jian-Xiang Zhu, Bo Jiang, Ying-Chun Chen, Wei Du, Ru-Jie Yan |
| Quelle: | Journal of the American Chemical Society. 143:4809-4816 |
| Verlagsinformationen: | American Chemical Society (ACS), 2021. |
| Publikationsjahr: | 2021 |
| Schlagwörter: | Asymmetric, orbital, compatibility, bond, Biochemistry, DFT, 01 natural sciences, π- Lewis base, ene addition, basis, vinylogous activation, Cancer, antibonding, density, nucleophilic group, π- allylpalladium species, Palladium Complex, mode, control experiments, Activating, cascade, back-bonding, imine, complex, Biotechnology, HOMO, uncoordinated, Chemical Sciences not elsewhere classified, Biophysics, vinylogy, difunctionalization, electron-deficient polyenes, furnishing, d-orbital, Genetics, Molecular Biology, alkylation, calculation, principle, Computational Biology, hydrodienylation reaction enantiose, Cell Biology, diene, 0104 chemical sciences, reactive partner, η 2 coordination, Catalyst, η 2 fashion, chemoselective, Developmental Biology |
| Beschreibung: | Here we report that palladium(0) complexes can coordinate in a η2 fashion to 1,3-dienes and significantly raise the energy of their highest occupied molecular orbital (HOMO) by donating the electrons from the d-orbitals to the empty antibonding molecular orbitals of double bonds (π*) via back-bonding. Thus, the uncoordinated double bond, as a more reactive partner on the basis of the principle of vinylogy, can directly attack imines, furnishing a formal hydrodienylation reaction enantioselectively. A chemoselective cascade vinylogous addition/allylic alkylation difunctionalization process between 1,3-dienes and imines with a nucleophilic group is also compatible, by trapping in situ formed π-allylpalladium species after initial ene addition. This π-Lewis base catalytic mode, featuring simple η2coordination, vinylogous activation, and compatibility with both conjugated neutral polyenes and electron-deficient polyenes, is elucidated by control experiments and density functional theory (DFT) calculations. |
| Publikationsart: | Article |
| Sprache: | English |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.1c01420 |
| DOI: | 10.1021/jacs.1c01420.s001 |
| Zugangs-URL: | https://pubmed.ncbi.nlm.nih.gov/33730847 https://pubs.acs.org/doi/pdf/10.1021/jacs.1c01420 https://pubmed.ncbi.nlm.nih.gov/33730847/ https://www.ncbi.nlm.nih.gov/pubmed/33730847 |
| Rights: | STM Policy #29 CC BY NC |
| Dokumentencode: | edsair.doi.dedup.....34f271de840700d56ac40e053e88e0a5 |
| Datenbank: | OpenAIRE |
Nájsť tento článok vo Web of Science | Abstract: | Here we report that palladium(0) complexes can coordinate in a η2 fashion to 1,3-dienes and significantly raise the energy of their highest occupied molecular orbital (HOMO) by donating the electrons from the d-orbitals to the empty antibonding molecular orbitals of double bonds (π*) via back-bonding. Thus, the uncoordinated double bond, as a more reactive partner on the basis of the principle of vinylogy, can directly attack imines, furnishing a formal hydrodienylation reaction enantioselectively. A chemoselective cascade vinylogous addition/allylic alkylation difunctionalization process between 1,3-dienes and imines with a nucleophilic group is also compatible, by trapping in situ formed π-allylpalladium species after initial ene addition. This π-Lewis base catalytic mode, featuring simple η2coordination, vinylogous activation, and compatibility with both conjugated neutral polyenes and electron-deficient polyenes, is elucidated by control experiments and density functional theory (DFT) calculations. |
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| ISSN: | 15205126 00027863 |
| DOI: | 10.1021/jacs.1c01420 |