�-silyl-a,�-unsaturated carbonyl compounds are versatile intermediates in the synthesis of complex molecules used in medicine and materials science. Previous methodologies to synthesize �-silyl-a,�-unsaturated carbonyl compounds employ harsh reaction conditions and often exhibit limited substrate scope. In this presentation, we will disclose a method to synthesize �-silyl-a,�-unsaturated esters, amides, ketones, and aldehydes that is diastereoselective, performed at room temperature, open-to-air, and uses water as the reaction solvent. Employing catalytic amounts of an inexpensive copper (II) salt and amine base, the reaction is complete within 2-4 hours. Using a,�-acetylenic esters and amides as substrates afford the products with complete (E)-selectivity in 82-99% yields. In contrast, �-silyl-a,�-unsaturated ketones and aldehydes provide the (Z)-isomers with high selectivity. Mechanistic insights for the observed diastereoselectivity will also be presented.

Copper(II)-catalyzed silylation of internal alkynes in water: Highly diastereoselective access to �-silyl-a,�-unsaturated carbonyl compounds

246th National Meeting (2013)

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