Selectivity Control in 3d Transition Metal-Catalyzed C–H Activation

Loup, Joachim

dc.contributor.advisor	Ackermann, Lutz Prof. Dr.
dc.contributor.author	Loup, Joachim
dc.date.accessioned	2019-08-23T09:32:34Z
dc.date.available	2019-08-23T09:32:34Z
dc.date.issued	2019-08-23
dc.identifier.uri	http://hdl.handle.net/21.11130/00-1735-0000-0003-C19E-1
dc.identifier.uri	http://dx.doi.org/10.53846/goediss-7617
dc.language.iso	eng	de
dc.publisher	Niedersächsische Staats- und Universitätsbibliothek Göttingen	de
dc.rights.uri	http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject.ddc	540	de
dc.title	Selectivity Control in 3d Transition Metal-Catalyzed C–H Activation	de
dc.type	doctoralThesis	de
dc.contributor.referee	Ackermann, Lutz Prof. Dr.
dc.date.examination	2019-08-16
dc.description.abstracteng	Methods for the selective functionalization of otherwise inert C–H bonds have been recognized as a transformative tool in synthetic organic chemistry, with applications ranging from the synthesis of complex bioactive compounds to material sciences. In particular, 3d metal catalysts have emerged in recent years as inexpensive, earth-abundant and less toxic alternatives to their heavier counterparts. However, full selectivity control in base metal-catalyzed C–H activation continues to be challenging. In this context, the development of novel 3d transition metal catalysts enabling chemo- and stereo-selective C–H functionalizations should be investigated. Within this thesis, we became interested in the development of a user-friendly and broadly applicable protocol for synthetically useful cobalt-catalyzed C–H amidations with ample substrate scope. Furthermore, while the enantioselective functionalization of C–H bonds remains largely dominated by noble transition metal catalysts such as palladium, rhodium and iridium, we developed an unprecedented enantioselective iron-catalyzed C–H alkylation by alkene hydroarylation. The design of novel chiral N-heterocyclic carbene (NHC) ligands proved to be crucial to achieve high enantioselectivities. Furthermore, detailed mechanistic studies were conducted to unravel the nature and mode of action of the in situ generated catalyst. Recently, nickel-catalyzed hydroarylation-type C–H activation has emerged as a cost-efficient alternative to expensive rhodium catalysis. However, the intramolecular hydroarylations of unactivated alkenes remain strongly limited by the requirement of pyrophoric organoaluminium additives, significantly compromising their functional group tolerance and synthetic utility. This observation prompted us to investigate the asymmetric cyclization of N-homoallylimidazoles under aluminium-free conditions. Interestingly, the endo product was selectively obtained, which in sharp contrast to previously reported methods. Mechanistic studies were then conducted in order to delineate the unique reactivity of the developed catalytic system.	de
dc.contributor.coReferee	Breder, Alexander Dr.
dc.contributor.thirdReferee	Alcarazo, Manuel Prof. Dr.
dc.contributor.thirdReferee	Tietze, Lutz Prof. Dr. Dr.
dc.contributor.thirdReferee	Das, Shoubhik Dr.
dc.contributor.thirdReferee	Stalke, Dietmar Prof. Dr.
dc.subject.eng	C–H Activation	de
dc.subject.eng	Catalysis	de
dc.subject.eng	Transition metal catalysis	de
dc.subject.eng	Asymmetric catalysis	de
dc.subject.eng	iron catalysis	de
dc.subject.eng	nickel catalysis	de
dc.subject.eng	cobalt catalysis	de
dc.subject.eng	mechanistic studies	de
dc.subject.eng	Hydroarylation	de
dc.subject.eng	chiral ligand	de
dc.subject.eng	3d transition metals	de
dc.subject.eng	Mössbauer spectroscopy	de
dc.subject.eng	Amidation	de
dc.identifier.urn	urn:nbn:de:gbv:7-21.11130/00-1735-0000-0003-C19E-1-5
dc.affiliation.institute	Fakultät für Chemie	de
dc.subject.gokfull	Chemie (PPN62138352X)	de
dc.identifier.ppn	1672307686

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