title: Orthogonal Pd- and Cu-based catalyst systems for C- and N-arylation of oxindoles.
abstract: In the cross-coupling reactions of unprotected oxindoles with aryl halides, Pd- and Cu-based catalyst systems displayed orthogonal chemoselectivity. A Pd-dialkylbiarylphosphine-based catalyst system chemoselectively arylated oxindole at the 3 position, while arylation occurred exclusively at the nitrogen using a Cu-diamine-based catalyst system. Computational examination of the relevant L1Pd(Ar)(oxindolate) and diamine-Cu(oxindolate) species was performed to gain mechanistic insight into the controlling features of the observed chemoselectivity.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Ryan A
authors.initials: RA
authors.lastname: Altman
authors.forename: Alan M
authors.initials: AM
authors.lastname: Hyde
authors.forename: Xiaohua
authors.initials: X
authors.lastname: Huang
authors.forename: Stephen L
authors.initials: SL
authors.lastname: Buchwald
mesh_terms: D001555:Benzene Derivatives / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D006846:Hydrocarbons, Halogenated / Q000737:chemistry; D007211:Indoles / Q000138:chemical synthesis / Q000737:chemistry*; D008024:Ligands; D009942:Organometallic Compounds / Q000737:chemistry; D000078183:Oxindoles; D010165:Palladium / Q000737:chemistry*; D011760:Pyrrolidinones / Q000138:chemical synthesis / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D001555:Benzene Derivatives; D006846:Hydrocarbons, Halogenated; D007211:Indoles; D008024:Ligands; D009942:Organometallic Compounds; D000078183:Oxindoles; D011760:Pyrrolidinones; C022960:2-oxindole; D010165:Palladium; D003300:Copper