1, 3-polyol containing natural products are a diverse class of molecules that frequently display extremely potent biological activities. Nature uses its biosynthetic machinery to assemble these polyols by sequential Claisen condensation, reduction and epimerization steps controlled by polyketide synthases. Inspired by the efficacy of these production lines, recent advances in synthetic methods have focussed on iterative, catalytic methods to rapidly assemble complex stereochemical arrays of 1,3-polyols. Over the last 5 years, our group has developed a new reactivity principle based on the union of copper complexes and diaryliodonium salts to form Cu(III)-aryl intermediates, a catalytically generated aromatic electrophile equivalent, that can engage a wide range of hydrocarbon nucleophiles to create important carbon-aryl bonds. As part of these studies, we found that simple alkenes underwent arylation of the carbon-carbon double bond via a species that displays carbocation-like properties.We reasoned that this reactive species could be intercepted with a nucleophile, thereby affecting an overall alkene difunctionalization process.This abstract describes application of this concept to the development of a new copper-catalyzed oxy-vinylation of readily available homo-allylic alcohol derivatives to produce 1, 3, 5�n syn-polyol fragments that can be readily transformed into natural product frameworks.

Copper-catalyzed difunctionalization of alkenes as a new strategy for the rapid synthesis of 1, 3, 5�n polyols

248th National Meeting (2014)

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