Development and application of metal catalyzed transfer hydrogenative C-C bond forming reactions




Waldeck, Andrew Robert

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While 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.



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