title: Amide enolate additions to acylsilanes: in situ generation of unusual and stereoselective homoenolate equivalents.
abstract: The synthesis of beta-hydroxy carbonyl compounds is an important goal due to their prevalence in bioactive molecules. A novel approach to construct these structural motifs involves the multicomponent reaction of acylsilanes, amides, and electrophiles. The addition of amide enolates to acylsilanes generates beta-silyloxy homoenolate reactivity by undergoing a 1,2-Brook rearrangement. These unique nucleophiles formed in situ can then undergo addition to alkyl halides, aldehydes, ketones, and imines. The gamma-amino-beta-hydroxy amide products derived from the addition of these homoenolates to N-diphenylphosphinyl imines are generated with excellent diastereoselectivity (> or = 20:1) and can be efficiently converted to highly valuable gamma-lactams. Finally, the use of optically active amide enolates delivers beta-hydroxy amide products with high levels of diastereoselectivity (> or = 10:1).
authors.affiliation: Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA.
authors.forename: Robert B
authors.initials: RB
authors.lastname: Lettan
authors.forename: Chris V
authors.initials: CV
authors.lastname: Galliford
authors.forename: Chase C
authors.initials: CC
authors.lastname: Woodward
authors.forename: Karl A
authors.initials: KA
authors.lastname: Scheidt