The chemistry of vicinal tricarbonyls and related systems

In this Account, we survey our work on the chemistry of vicinal tricarbonyls and cyano analogues. Methods of preparing the vicinal functionalities are reviewed as well as the use in organic synthesis of these strongly electrophilic aggregates, readily available from carboxylic acids. By attaching neighboring electrophilic groups to the vicinal tricarbonyl, we have developed polyelectrophilic systems, which may be added to di- and trinucleophiles to create novel types of multistep reactivity. Application of tricarbonyl chemistry in synthesis is illustrated by the formation of various natural products or their precursors including fused-ring beta-lactams, indole alkaloids, marine metabolites, enzyme inhibitors containing alpha-keto amides, and bioactive depsipeptides incorporating hydrated tricarbonyl units.