Chapter 5: Vanadium(v)-induced Oxidative Cross-coupling of Enolate Species

The selective intermolecular oxidative cross-coupling of enolates provides a potentially direct method for the synthesis of unsymmetrical 1,4-dicarbonyl compounds, which are common substructures found in natural products and pharmaceuticals and their synthetic intermediates, as well as building blocks for the construction of various heterocyclic compounds. The main point of this reaction is achieving selective cross-coupling, as well as minimizing undesired homocoupling. The proposed strategy depends on the selective one-electron oxidation of one enolate, resulting in a Lewis acid-activated electrophilic carbonyl α-radical species, followed by trapping with another enolate. This chapter summarizes the oxovanadium(v)-induced oxidative cross-coupling of enolates between boron and silyl enolates that have been developed in the author's studies.