title: Brønsted acid catalyzed enantioselective indole aza-Claisen rearrangement mediated by an arene CH-O interaction.
abstract: Although the aromatic aza-Claisen rearrangement is a general strategy for accessing substituted aromatic amines, there are no highly enantioselective examples of this process. We report the first Brønsted acid catalyzed enantioselective indole aza-Claisen rearrangement for the synthesis of chiral 3-amino-2-substituted indoles. We present evidence for an arene CH-O interaction as a source of activation and stereoinduction, which is an unprecedented phenomenon in enantioselective Brønsted acid catalysis. The products of this reaction can be transformed into 3-aminooxindoles, which are prevalent in many biologically active small molecules.
authors.affiliation: Department of Biochemistry, The University of Texas Southwestern Medical Center at Dallas , 5323 Harry Hines Boulevard, Dallas, Texas 75390-9038, United States.
authors.forename: Pradip
authors.initials: P
authors.lastname: Maity
authors.forename: Ryan P
authors.initials: RP
authors.lastname: Pemberton
authors.forename: Dean J
authors.initials: DJ
authors.lastname: Tantillo
authors.forename: Uttam K
authors.initials: UK
authors.lastname: Tambar
mesh_terms: D000143:Acids / Q000737:chemistry*; D001555:Benzene Derivatives / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D000143:Acids; D001555:Benzene Derivatives; D007211:Indoles