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DOI: 10.1055/s-2008-1042666
Hartwig-Buchwald Amination on Solid Supports
Contributor(s):Yasuhiro Uozumi, Yoichi M. A. Yamada, Toshihiro WatanabeUniversität Karlsruhe, Germany
Hartwig-Buchwald Amination on Solid Supports: A Novel Access to a Diverse Set of 1H-Benzotriazoles
J. Comb. Chem. 2007, 9: 1114-1137
Publication History
Publication Date:
21 February 2008 (online)
Key words
Hartwig-Buchwald amination - solid supports - 1H-benzotriazoles
Significance
The solid-phase synthesis of N-substituted benzotriazoles via the Hartwig-Buchwald reaction was reported. Thus, the ortho-halo and ortho-aminoarene triazene resins 1, 2, and 4 were prepared from aryl diazonium salts and benzylaminomethyl polystyrene. The Hartwig-Buchwald reactions of 1 with amines, and 4 with haloarenes were carried out with a Pd catalyst to give the corresponding triazene-linked N-substituted 2-anilines 5. 1H-Benzotriazoles 6 were obtained under mild acidic conditions via ortho-aminoarene diazonium salts (36 examples; 1-88% yield, 60-99% purity).
Comment
The Hartwig-Buchwald cross-coupling is a palladium-catalyzed reaction of aryl halides with amines to afford the corresponding anilines, which has become a powerful tool in solid-phase organic synthesis (selected pioneering works: Y. D. Ward, V. Farina Tetrahedron Lett. 1996, 37, 6993; C. A. Willoughby, K. T. Chapman Tetrahedron Lett. 1996, 37, 7181). The palladium catalysts were prepared from Pd2(dba)3 or Pd(OAc)2 as Pd sources and rac-BINAP or 2-(dicyclohexylphosphino)biphenyl as ligands. Benzotriazoles are the parent materials for the production of UV absorbers.