title: Efficient Access to Chiral Trisubstituted Aziridines via Catalytic Enantioselective Aza-Darzens Reactions.
abstract: Herein, we report a Zn-ProPhenol catalyzed aza-Darzens reaction using chlorinated aromatic ketones as nucleophilic partners for the efficient and enantioselective construction of complex trisubstituted aziridines. The α-chloro-β-aminoketone intermediates featuring a chlorinated tetrasubstituted stereocenter can be isolated in high yields and selectivities for further derivatization. Alternatively, they can be directly transformed to the corresponding aziridines in a one-pot fashion. Of note, the reaction can be run on gram-scale with low catalyst loading without impacting its efficiency. Moreover, this methodology was extended to α-bromoketones which are scarcely used in enantioselective catalysis because of their sensitivity and lack of accessibility.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA, 94305-5080, USA.
authors.forename: Barry M
authors.identifier: 0000-0001-7369-9121
authors.initials: BM
authors.lastname: Trost
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA, 94305-5080, USA.
authors.forename: Tanguy
authors.identifier: 0000-0003-0006-5229
authors.initials: T
authors.lastname: Saget
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA, 94305-5080, USA.
authors.forename: Chao-I Joey
authors.initials: CJ
authors.lastname: Hung
mesh_terms: D001372:Aza Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D001388:Aziridines / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D054879:Halogenation; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry; D010636:Phenols / Q000737:chemistry; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry*
chemical_list: D001372:Aza Compounds; D001388:Aziridines; D007659:Ketones; D010636:Phenols; D015032:Zinc
keywords: Mannich reaction; Zn-ProPhenol; asymmetric catalysis; aza-Darzens reaction; tertiary chloride