Krische, Michael J.2016-08-232018-01-222016-08-232018-01-222016-05May 2016http://hdl.handle.net/2152/39609While polyketides display a diverse range of biological properties and are used extensively in human medicine, a lack of methods for the concise preparation of these complex structures still poses a significant challenge in the field of synthetic organic chemistry. To address this issue, metal catalyzed methods for transfer hydrogenative C-C bond formation have been developed. These methods construct products of carbonyl addition through direct C-H bond functionalization, which provides a more atom economic and efficient approach to carbonyl addition products and circumvents the need for stoichiometric use of chiral auxiliaries, premetallated C-nucleophiles, and discrete alcohol-to-carbonyl redox reactions. Efforts have been focused on the development of ruthenium-catalyzed coupling reactions of secondary alcohols to basic chemical feedstocks as well as the application of iridum-catalyzed couplings of primary alcohols with π-unsaturates in the context of the total syntheses of (−)-cyanolide A and (+)-cryptocaryol A. These total syntheses represent the most concise route reported to date for each natural product and illustrate the synthetic utility of transfer hydrogenative C-C bond forming methodology.application/pdfCatalysisSpirolactoneTotal synthesisCyanolideCryptocaryolThesis2016-08-23