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Ligand-controlled selectivity in palladium(0)-catalyzed C(sp2)-C(sp3) Negishi cross-coupling reactions

Zhang, Ke-Feng. Ligand-controlled selectivity in palladium(0)-catalyzed C(sp2)-C(sp3) Negishi cross-coupling reactions. 2018, Doctoral Thesis, University of Basel, Faculty of Science.

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Official URL: http://edoc.unibas.ch/diss/DissB_12830

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Abstract

Over the past decades, transition-metal-catalyzed cross-coupling reactions have witnessed considerable growth and emerged as a powerful tool for the construction of carbon-carbon bonds. These reactions have found numerous applications in assembling structurally complex molecules ranging from medicines to materials. While the C(sp2)-C(sp2) cross-coupling reactions have seen a tremendous development, less effort has been devoted to the more challenging C(sp2)-C(sp3) couplings.
The selectivity control in the palladium(0)-catalyzed cross-coupling of alkyl nucleophiles is an important topic of research in the Baudoin group. Both direct and migrative cross-couplings can be achieved by simply switching the ligand involved.
Following the long-standing interest in this field, we firstly extended the migrative cross-coupling reactions to simple and easily available secondary alkyl bromides under Barbier conditions. Moreover, the terminal-selective functionalization of simple alkanes could be achieved when this reaction was coupled to a non-selective radical monobromination process.
On the other hand, a series of azole-based bulky phosphine ligands was designed and applied to direct C(sp2)-C(sp3) Barbier-Negishi cross-coupling reactions, successfully preventing the β-hydride elimination process while favouring the direct reductive elimination.
Finally, the ‘‘ligand-controlled selectivity’’ strategy was applied to the divergent synthesis of enantioenriched β-amino acid derivatives.
Advisors:Baudoin, Olivier and Leroux, Frédéric
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Synthetische Chemie (Baudoin)
UniBasel Contributors:Zhang, Ke-Feng and Baudoin, Olivier
Item Type:Thesis
Thesis Subtype:Doctoral Thesis
Thesis no:12830
Thesis status:Complete
Bibsysno:Link to catalogue
Number of Pages:1 Online-Ressource (468 Seiten)
Language:English
Identification Number:
Last Modified:22 Nov 2018 05:30
Deposited On:21 Nov 2018 15:12

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