title: Palladium-catalyzed [3,3]-rearrangement for the facile synthesis of allenamides.
abstract: A [3,3]-rearrangement that is used for facile construction of chiral allenamides is described. A propargylic alcohol, a chlorophosphite, and Cbz-azide are combined to provide a propargylic phosphorimidate that, in the presence of catalytic palladium(II), rearranges to an allenamide. By varying the substitution pattern on the propargylic alcohol, mono-, di-, and trisubstituted allenamides can be accessed in good yields. Additionally, the use of an enantiomerically enriched propargylic alcohol enables the preparation of stereochemically defined allenamides.
authors.affiliation: Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA.
authors.forename: Amy M
authors.initials: AM
authors.lastname: Danowitz
authors.forename: Christopher E
authors.initials: CE
authors.lastname: Taylor
authors.forename: Tamar M
authors.initials: TM
authors.lastname: Shrikian
authors.forename: Anna K
authors.initials: AK
authors.lastname: Mapp
mesh_terms: D000480:Alkynes / Q000737:chemistry; D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D017905:Phosphites / Q000737:chemistry; D020005:Propanols / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000480:Alkynes; D000577:Amides; D017905:Phosphites; D020005:Propanols; D010165:Palladium; C028255:propargyl alcohol