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Pd(0)-catalyzed arylation of O-carbamates via Negishi cross-coupling and intermolecular Pd(0)-catalyzed atroposelective Csp2-H bond activation

Royal, Titouan. Pd(0)-catalyzed arylation of O-carbamates via Negishi cross-coupling and intermolecular Pd(0)-catalyzed atroposelective Csp2-H bond activation. 2018, Doctoral Thesis, University of Basel, Faculty of Science.

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Official URL: http://edoc.unibas.ch/diss/DissB_12974

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Abstract

Over the past decades, the transition-metal catalyzed C-H bond functionalization has emerged as a powerful tool for the straightforward access to molecular complexity, while respecting the principles of atom- and step-economy.
The research at the Baudoin group mainly focuses on the activation and the functionalization of C-H bonds with palladium. The investigation led to the development of new methodologies including intramolecular Csp3-H bond activation, and the arylation of remote Csp3-H bond via migrative cross-couplings. These methodologies were applied in the synthesis of biologically active complex molecules.
The ligand-controlled regioselective arylation of cyclic and acyclic N-Boc-amines via Pd(0)-catalyzed migrative Negishi cross-coupling was recently developed within our group. In light of this work, the enantioselective a-arylation of O-carbamates was achieved by combining Hoppe’s sparteine-mediated enantioselective lithiation-deprotonation and Pd(0)-catalyzed Negishi cross-coupling.
We then focused on the ligand-controlled migrative arylation of O-carbamates. The attempts toward the selective b-arylation were unsuccessful but led us to the discovery of a ligand-controlled g-arylation of g,d-unsatured O-carbamates. The reaction proceeds via a non-canonical haptotropic rearrangement of the palladium intermediate.
As a follow-up, we examined the feasibility of an intermolecular Pd(0)-catalyzed atroposelective Csp2-H arylation. Our investigation led us to the discovery of a catalytic system involving newly introduced bifunctionnal ligands.
Advisors:Baudoin, Olivier and Sparr, Christof
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Synthetische Chemie (Baudoin)
UniBasel Contributors:Baudoin, Olivier and Sparr, Christof
Item Type:Thesis
Thesis Subtype:Doctoral Thesis
Thesis no:12974
Thesis status:Complete
Bibsysno:Link to catalogue
Number of Pages:1 Online-Ressource (539 Seiten)
Language:English
Identification Number:
Last Modified:27 Mar 2019 05:30
Deposited On:26 Mar 2019 13:17

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