Carbon-carbon bond formation lies at the heart of chemical synthesis. Research in the Krische laboratory reveals that C-C bonds can be formed under the conditions of catalytic hydrogenation. This concept is extended further via “C-C bond forming transfer hydrogenations” and related hydrogen auto-transfer processes, wherein hydrogen exchange between alcohols and π-unsaturated reactants triggers generation of aldehyde-organometal pairs that combine to give products of carbonyl addition. Direct alcohol CH-functionalization <i>via</i> redox-triggered carbonyl addition enhances efficiency by merging alcohol-to-aldehyde redox reactions with C-C bond construction events. This new pattern of reactivity enables the direct C-C coupling of π-unsaturated reactants to renewable alcohols (methanol, ethanol and glycerol) to furnish higher alcohols, and has been applied to the construction of diverse polyketide natural products (bryostatin, roxaticin, 6-deoxyerythronolide, trienomycin, cyanolide, etc.).

Alcohol C-H functionalization via redox-triggered Carbonyl Addition: Borrowing hydrogen, returning carbon

249th National Meeting (2015)

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