title: Phosphoramidite gold(I)-catalyzed diastereo- and enantioselective synthesis of 3,4-substituted pyrrolidines.
abstract: In this article the utility of phosphoramidite ligands in enantioselective Au(I) catalysis was explored in the development of highly diastereo- and enantioselective Au(I)-catalyzed cycloadditions of allenenes. A Au(I)-catalyzed synthesis of 3,4-disubstituted pyrrolidines and γ-lactams is described. This reaction proceeds through the enantioselective Au(I)-catalyzed cyclization of allenenes to form a carbocationic intermediate that is trapped by an exogenous nucleophile, resulting in the highly diastereoselective construction of three contiguous stereogenic centers. A computational study (DFT) was also performed to gain some insight into the underlying mechanisms of these cycloadditions. The utility of this new methodology was demonstrated through the formal synthesis of (-)-isocynometrine.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA.
authors.forename: Ana Z
authors.initials: AZ
authors.lastname: González
authors.forename: Diego
authors.initials: D
authors.lastname: Benitez
authors.forename: Ekaterina
authors.initials: E
authors.lastname: Tkatchouk
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D006046:Gold / Q000737:chemistry*; D007093:Imidazoles / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009943:Organophosphorus Compounds / Q000737:chemistry*; D011759:Pyrrolidines / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D000470:Alkaloids; D007093:Imidazoles; D009943:Organophosphorus Compounds; D011759:Pyrrolidines; C445724:isocynometrine; C434331:phosphoramidite; D006046:Gold