Alkene hydroformylation is the largest volume application of homogenous metal catalysis and the prototypical C-C bond forming hydrogenation. Despite the impact of hydroformylation, systematic efforts to generalize this process were absent at the onset of our studies. Using cationic rhodium and iridium catalysts, we find that diverse p-unsaturated reactants reductively couple to carbonyl compounds and imines under hydrogenation conditions, offering a byproduct-free alternative to stoichiometric organometallics in a range of classical C=X (X = O, NR) addition processes. This concept is extended further via �C-C bond forming transfer hydrogenation�. Here, using ruthenium or iridium catalysts, alcohols serve dually as hydrogen donors and aldehyde precursors, enabling carbonyl addition directly from the alcohol oxidation level in the absence of stoichiometric byproducts. Concise total syntheses of bryostatin, roxaticin and 6-deoxyerythronolide B are achieved based on this new language for organic synthesis. 

Formation of C-C bonds via catalytic hydrogenation and transfer hydrogenation: Merged redox-construction events for organic synthesis

244th National Meeting (2012)

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