title: Highly regioselective Pd-catalyzed intermolecular aminoacetoxylation of alkenes and evidence for cis-aminopalladation and S(N)2 C-O bond formation.
abstract: Synthetic methods that achieve oxidative 1,2-difunctionalization of alkenes are very powerful in organic chemistry. Here we report the first examples of intermolecular Pd-catalyzed aminoacetoxylation of alkenes with phthalimide as the nitrogen source and PhI(OAc)2 as the stoichiometric oxidant and source of acetate. These reactions are highly regio- and diastereoselective, and mechanistic studies reveal that the reaction proceeds via cis-aminopalladation of the alkene followed by oxidative cleavage of the intermediate Pd-C bond with inversion of stereochemistry.
authors.affiliation: Department of Chemistry, University of Wisconsin--Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
authors.forename: Guosheng
authors.initials: G
authors.lastname: Liu
authors.forename: Shannon S
authors.initials: SS
authors.lastname: Stahl
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000586:Amination; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010797:Phthalimides / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D010797:Phthalimides; C037431:phthalimide; D010165:Palladium; D002244:Carbon; D010100:Oxygen