Trivalent phosphorus compounds are known to undergo condensation with 1,2-dicarbonyl species (Ramirez reaction) to form adducts formulated as either dioxaphospholenes or oxyphosphonium enolates. We describe the development of synthetic methods utilizing these Ramirez adducts as reactive intermediates. Specifically, we show that these adducts are subject to sequential attack by electrophiles and nucleophiles resulting in deoxygenative functionalization of the substrates with formation of two new geminal bonds. These reactions lead to various synthetically useful structural motifs. Asymmetric transformations can also be achieved via derivatization of phosphorus(III) reagents.

Phosphorus(III)-mediated geminal difunctionalization of 1,2-dicarbonyl compounds

248th National Meeting (2014)

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