title: SmI2-promoted Reformatsky-type coupling reactions in exceptionally hindered contexts.
abstract: Highly substituted, very hindered enones were synthesized using a two-step procedure that utilizes a diiodosamarium-promoted Reformatsky-type coupling and dehydration using Martin sulfurane. Both alpha-chloro- and alpha-bromoketones were coupled with a variety of carbonyl nucleophiles to form the intermediate beta-hydroxyketones, occurring with excellent diastereoselectivity, favoring the syn isomer (R1=Me). This technique complements other methods and enables the preparation of enones outside of the scope of current olefination methodology.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Brian A
authors.initials: BA
authors.lastname: Sparling
authors.forename: Ryan M
authors.initials: RM
authors.lastname: Moslin
authors.forename: Timothy F
authors.initials: TF
authors.lastname: Jamison
mesh_terms: D012493:Samarium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D012493:Samarium