title: Gold(I)-catalyzed diastereo- and enantioselective 1,3-dipolar cycloaddition and Mannich reactions of azlactones.
abstract: Azlactones participate in stereoselective reactions with electron-deficient alkenes and N-sulfonyl aldimines to give products of 1,3-dipolar cycloaddition and Mannich addition reactions, respectively. Both of these reactions proceed with good to excellent diastereo- and enantioselectivity using a single class of gold catalysts, namely C(2)-symmetric bis(phosphinegold(I) carboxylate) complexes. The development of the azlactone Mannich reaction to provide fully protected anti-α,β-diamino acid derivatives is described. 1,3-Dipolar cycloaddition reactions of several acyclic 1,2-disubstituted alkenes and the chemistry of the resultant cycloadducts are examined to probe the stereochemical course of this reaction. Reaction kinetics and tandem mass spectrometry studies of both the cycloaddition and Mannich reactions are reported. These studies support a mechanism in which the gold complexes catalyze addition reactions through nucleophile activation rather than the more typical activation of the electrophilic reaction component.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California, 94720, United States.
authors.forename: Asa D
authors.initials: AD
authors.lastname: Melhado
authors.forename: Giovanni W
authors.initials: GW
authors.lastname: Amarante
authors.forename: Z Jane
authors.initials: ZJ
authors.lastname: Wang
authors.forename: Marco
authors.initials: M
authors.lastname: Luparia
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006046:Gold / Q000737:chemistry*; D007783:Lactones / Q000138:chemical synthesis*; D021241:Spectrometry, Mass, Electrospray Ionization; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D007783:Lactones; D006046:Gold