Alkene, Ketone, and Polyol Functionalization by Stereoselective Rhodium(I) and Copper(II) Catalysis

Developing transition metal catalysis for organic synthesis can have a profound impact on the manufacturing of polymers, agricultural agents, and pharmaceuticals. Over the last two to three decades, organic and organometallic chemists have discovered extraordinary reactivity with transition metals, applying it to important problems in biology, medicine, and materials. This thesis will describe the use of transition metals as catalysts for new synthetic reactions that transform simple starting materials into valuable enantioenriched products.;Chapters 1 and 2 describe the concepts of `chelation-control' and strain for the development of novel rhodium(I) catalyzed intermolecular alkene hydroacylations. The analogous reaction of ketones is less well-understood and is thus rare in the chemical literature. Chapters 3 and 4 discuss new advances in the field as well as the design and execution of the first enantioselective intermolecular aldehyde-ketone cross-coupling. Mechanistic studies point to a unique mechanism involving homobimetallic activation of the aldehyde. The first dynamic kinetic resolution (DKR) of allylic sulfoxides via rhodium(I) catalyzed hydrogenation is presented in chapter 5. Experimental and theoretical studies reveal that rhodium catalyzes both the racemization of the allylic sulfoxide starting material, as well as the alkene hydrogenation. Preliminary studies toward a DKR hydroacylation are briefly discussed. While there are many examples of alkene hydrogenations and hydroacylations, the related carboacylation reaction is underexplored due to difficulties in activating a C---C bond. Through insights gained from mechanistic studies in hydroacylation, preliminary studies on exploiting C---H activation for enantioselective carboacylation are described in chapter 6. Finally, the use of copper(II) catalysts to activate and acylate carbohydrate derivatives in a regioselective manner is included in Chapter 7.