title: Isolable analogues of the Breslow intermediate derived from chiral triazolylidene carbenes.
abstract: Since Breslow's initial report on the thiamine mode of action, the study of catalytic acyl carbanion processes has been an area of immense interest. With the advent of azolylidene catalysis, a plethora of reactivtiy has been harnessed, but the crucial nucleophilic intermediate proposed by Breslow had never been isolated or fully characterized. Herein, we report the isolation and full characterization of nitrogen analogues of the Breslow intermediate. Both stable and catalytically relevant, these species provide a model system for the study of acyl carbanion and homoenolate processes catalyzed by triazolylidene carbenes.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
authors.forename: Daniel A
authors.initials: DA
authors.lastname: DiRocco
authors.forename: Kevin M
authors.initials: KM
authors.lastname: Oberg
authors.forename: Tomislav
authors.initials: T
authors.lastname: Rovis
mesh_terms: D000838:Anions / Q000737:chemistry; D002384:Catalysis; D002621:Chemistry / Q000379:methods*; D003460:Crystallization; D018360:Crystallography, X-Ray / Q000379:methods; D007477:Ions; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry; D011336:Probability; D013237:Stereoisomerism; D013696:Temperature; D013831:Thiamine / Q000737:chemistry; D014230:Triazoles / Q000737:chemistry*
chemical_list: D000838:Anions; D007477:Ions; D014230:Triazoles; C030011:carbene; D009584:Nitrogen; D008697:Methane; D013831:Thiamine