C–H and C–F Activation by Manganese, Nickel and Ruthenium Catalysis

by Valentin Müller
Doctoral thesis
Date of Examination:2021-03-29
Date of issue:2021-04-19
Advisor:Prof. Dr. Lutz Ackermann
Referee:Prof. Dr. Lutz Ackermann
Referee:Prof. Dr. Shoubhik Das
Referee:Prof. Dr. Konrad Koszinowski
Referee:Prof. Dr. Dietmar Stalke
Referee:Prof. Dr. Johannes C. L. Walker
Referee:Dr. Holm Frauendorf
Persistent Address: http://dx.doi.org/10.53846/goediss-8541

 

 

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Abstract

English

The development of novel environment-friendly, step- and atom-economical methodologies is one of the main goals in organic chemistry. In this context, the direct functionalization of inert C–(Het) and C–H bonds has emerged as an environmentally-benign alternative that avoids lengthy syntheses and stoichiometric amounts of waste, and has therefore attracted broad interest with applications also to chemical industries. In this thesis, several methods have been devised in terms of efficiency, diversity and sustainability. In this context, nickel-catalyzed C–F alkylations by a novel bidentate SPO/nickel catalyst and enantioselective aluminum-free alkene hydroarylations via C–H activation by a chiral nickel/JoSPOphos manifold were developed. Furthermore, C−H/C−F functionalizations, via earth-abundant manganese catalysis, set the stage for a variety of step-economical (per)fluoro allylations and alkenylations exclusively resulting in the forming of the (Z)-isomer. Moreover, ruthenium(II)-catalyzed hydrogen isotope exchange (HIE) of various carboxylic acids, as well as active pharmazeutical ingredients (APIs) were developed, yielding deuterium and tritium labeled scaffolds. Finally, a hybrid ruthenium catalyst for meta C−H alkylations in a reusable manner with broad applicability was developed.
Keywords: C–H Activation; Catalysis; Asymmetric catalysis; 3d transition metals; C–F Activation; Heterogeneous catalysis; Hydrogen Isotope Exchange (HIE); Active Pharmaceutical Ingredient (API); Nickel catalysis; Manganese catalysis; Ruthenium catalysis
 
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