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Synthesis and Application of Chiral Palladium-Phosphane Precatalyst in Enantioselective C-N Cross-Coupling

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posted on 23.05.2021, 11:54 by Nande Abena Wright
The various strategies and reaction conditions towards the synthesis of benzene-, naphthalene-, and phenanthrene-based dicyclohexylbiaryl phosphanes are presented. A chiral third generation Buchwald-type precatalyst has been synthesized, employing the non-commercially available ligand, (R)-dicyclohexyl(2'-methoxy-[1,1'-binaphth-2-yl])phosphane, (R)-Cy2MOP, and a dimeric methanesulfonate-bridged palladacycle based on a 2-aminobiphenyl scaffold. Application of the palladacyclic precatalyst in an enantioselective variant of the BuchwaldHartwig reaction is demonstrated in the desymmetrization of prochiral α-(2-bromobenzyl)malonamides via intramolecular N-arylation. The scope of the catalysis in the presence of the precatalyst has been investigated with efforts towards optimizing yields, catalyst loading, and enantioselectivities. Attempts towards the isolation of a potential reaction intermediate in the form of a stable amido-bound palladium complex are discussed. Finally, strategies towards gaining mechanistic insight on the origin of the enantiomeric excess are discussed.

History

Language

eng

Degree

Master of Science

Program

Molecular Science

Granting Institution

Ryerson University Viirre, Russell

LAC Thesis Type

Thesis