Alper, Howard,Aldea, Ioana Raluca.2009-03-232009-03-2319991999Source: Dissertation Abstracts International, Volume: 61-04, Section: B, page: 1950.9780612480827http://hdl.handle.net/10393/8579http://dx.doi.org/10.20381/ruor-15888This thesis describes a study of the hydrogenation of different functional groups in the presence of clays or metals anchored on clays as catalysts. The thesis also describes the selective aerobic oxidation of sulfides to sulfoxides using a palladium based catalyst. Chapters 2 and 3 detail work on the hydrogenation processes. Ruthenium clays were prepared using montmorillonite-phosphine or montmorillonite-bipyridine and RuCl3·H2O. The clays obtained were found to be effective catalysts for the reduction of unsaturated esters, epoxides, sulfones and phosphonates. It was shown that Ru-phosphine clay is an efficient catalyst for reduction of the alpha-carbonyl group of alpha-ketoesters and alpha-ketoamides, and the alpha-imine group of alpha-iminoesters and alpha-iminoketones. The reductive amination of alpha-ketoesters with amines, catalyzed by ruthenium clay, was studied. The diastereoselectivity of the reactions was studied using chiral amines. Modification of the clay structure using organic ligands and/or metals was also investigated. The reduction of aliphatic and aromatic ketones by hydrogen transfer was studied. The reaction was catalyzed by sodium montmorillonite and took place under basic conditions (0.06 M KOH in isopropanol). The cis /trans selectivity of the process was also examined. The last chapter (Chapter 4) describes the selective oxidation of sulfides to sulfoxides. The palladium complex [Pd(PBut2H)(mu-PBu t2)]2, on exposure to oxygen in tetrahydrofuran, generates an active catalytic system for this reaction. The presence of other functional groups (amide, carboxyl) does not interfere with the oxidation process at sulfur. It was shown that this process is stereospecific in the case of (+)-biotin-sulfoxide 4-nitrophenyl ester.194 p.Chemistry, Organic.Thesis