Orthogonal Pd- and Cu-based catalyst systems for C- and N-arylation of oxindoles.
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.
Altman
Ryan A
RA
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Hyde
Alan M
AM
Huang
Xiaohua
X
Buchwald
Stephen L
SL
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
D001555:Benzene Derivatives; D006846:Hydrocarbons, Halogenated; D007211:Indoles; D008024:Ligands; D009942:Organometallic Compounds; D000078183:Oxindoles; D011760:Pyrrolidinones; C022960:2-oxindole; D010165:Palladium; D003300:Copper