title: Tandem catalytic allylic amination and [2,3]-Stevens rearrangement of tertiary amines.
abstract: We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.
authors.affiliation: Department of Biochemistry, Division of Chemistry, The University of Texas Southwestern Medical Center at Dallas, 5323 Harry Hines Boulevard, Dallas, Texas 75390-9038, USA
authors.forename: Arash
authors.initials: A
authors.lastname: Soheili
authors.forename: Uttam K
authors.initials: UK
authors.lastname: Tambar
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry; D000586:Amination; D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D055601:Organic Chemistry Phenomena; D010165:Palladium / Q000737:chemistry
chemical_list: D000498:Allyl Compounds; D000588:Amines; D010165:Palladium