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Jacobsen, Eric N. Fields, Lisa Beattie 2014-12-17T21:29:11Z 2014-12-17T21:29:11Z 10000-01-01 1993 1993 In Part I of this thesis, a new class of optically active heterobimetallic complexes is described. The complexes L*MCl2 (M = Pt(II), Pd(II), L* = C2-symmetric boron containing bisphosphine ligand) and (Rh(cod)(L*)) ClO4 (cod = eta2,eta 2-1,5-cyclooctadiene) were synthesized as templates for asymmetric catalytic reactions that could involve substrate precoordination to a Lewis acidic site remote from the transition metal reaction site. Primary amines were found to bind reversibly via a nitrogen-boron interaction to the free ligands L*. 1H NMR measurements revealed that the binding constant of representative primary amines to L* could be tuned through variation of the electronic properties of the substituents covalently bound to boron. In Part II, the asymmetric synthesis of S-(+)-ibuprofen is described. The key asymmetry-inducing step was the catalytic epoxidation of 4-isobutylstyrene using household bleach as the terminal oxidant and chloro- (S,S)-[(2,2 '-((1,2-diphenyl-1,2-ethanediyl)bis(nitrilomethylidyne)) bis (6-(1,1-dimethylethyl)-4-methylphenolato))-N,N ', O,O'] manganese(III) as the catalyst. Enantioselectivities in the range of 50-63% were obtained using this or similar catalysts. The final product was obtained from the epoxide via treatment with trimethylaluminum followed by KMnO 4 oxidation. In Part III, the use of chiral Mn(III)salen complexes as asymmetric C-H activation catalysts for aryl alkanes was examined. Indanol was obtained from indan in 23% ee using household bleach as the terminal oxidant. Kinetic resolution of benzylic alcohols also occurred under reaction conditions, with enantioselectivities in the range of 2--20%. Made available in DSpace on 2014-12-17T21:29:11Z (GMT). No. of bitstreams: 1 9411619.pdf: 4392942 bytes, checksum: a90d7e1d97d91247709ca4d3f273aac0 (MD5) Previous issue date: 1993 Embargo set by: Seth Robbins for item 72458 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 118 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1993. http://hdl.handle.net/2142/72290 (UMI)AAI9411619 Chemistry, Organic Fundamental and Applied Studies in Asymmetric Catalysis text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.