Neely, Jamie M., authorRovis, Tomislav, advisorMcNally, Andrew, committee memberFisk, John D., committee memberNeilson, James R., committee memberInamine, Julia M., committee member2007-01-032007-01-032014http://hdl.handle.net/10217/88453Described herein are two complementary rhodium-catalyzed methods for the synthesis of substituted pyridines from unsaturated oxime derivatives and alkenes. In the first, formal [4+2] cycloaddition of O-pivaloyl α, β-unsaturated oxime esters and activated terminal alkenes was discovered to proceed in high yields and with excellent selectivity for 6-substituted pyridine products. Mechanistic experiments were found to be consistent with a reversible C-H activation step and a C-N bond forming, N-O bond cleaving process en route to pyridine formation. Rhodium-catalyzed coupling using unactivated alkene substrates was shown to present important information regarding the influence of the alkene component on product distribution. In a second method, access to 5-substituted pyridine derivatives was achieved by decarboxylative annulation of α, β-unsaturated oxime esters and β-substituted acrylic acid derivatives. In this case, carboxylic acids were found to serve as traceless activating groups for selective alkene incorporation. A wealth of mechanistic insight was gained by identification of and decomposition studies regarding catalytically relevant rhodium complexes.born digitaldoctoral dissertationsengCopyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright.rhodiumoxime esterspyridinesalkenesC-H activationText