title: Silver-Catalyzed Aldehyde Olefination Using Siloxy Alkynes.
abstract: We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.
authors.affiliation: Department of Chemistry, University of Chicago, 5735 S. Ellis Ave, Chicago, IL 60637 Phone (+1)-773-7026886, Fax (+1)-773-7020805.
authors.forename: Jianwei
authors.initials: J
authors.lastname: Sun
authors.forename: Valerie A
authors.initials: VA
authors.lastname: Keller
authors.forename: S Todd
authors.initials: ST
authors.lastname: Meyer
authors.forename: Sergey A
authors.initials: SA
authors.lastname: Kozmin
keywords: Chemoselectevity; Olefination; Siloxy Alkyne; Silver