Universität zu Köln

Brüllingen, Eric (2020). P-biphenyl-2,2’-bisfenchol phosphite (P-BIFOP-X) based palladium-, copper- and iron-catalysts in enantioselective C–C couplings. PhD thesis, Universität zu Köln.

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Abstract

P-biphenyl-2,2'-bisfenchol phosphite (P-BIFOP-X, X = H, D, F, Cl, N3, CN, and others) ligands used in enantioselective Pd-catalyzed Tsuji-Trost alkylations, enantioselective Cu-catalyzed 1,4-alkylations and enantioselective Fe-catalyzed 1,4-alkylations. Reaction mechanisms are explored by DFT-computations showing a hyperconjugation effect called F-switch for enantioselective Pd-catalyzed Tsuji-Trost alkylations, a preferred syn-conformation of the enone in enantioselective Cu-catalyzed 1,4-alkylations and a proposed reaction mechanism for the enantioselective Fe(I,III)-catalyzed 1,4-alkylations. Finally the sterical effect of large (Ph) or electronic (ester) groups are discussed for the photooxygenation Schenck-ene reaction and the DFT-computations reveal a bifurcation of the transition state preferring a certain reaction path forming a specific product.