Synthesis and characterizations of N,N′-bis(diphenylphosphino)-2-(aminomethyl)aniline derivatives: application of a palladium(II) complex as pre-catalyst in Heck and Suzuki cross-coupling reactions

The reaction of 2-(aminomethyl)aniline with 2 equivalents of PPh2Cl in the presence of Et3N, proceeds in CH2Cl2 to give N,N'-bis(diphenyl phosphino)-2-(aminomethyl)ani line 1 in good yield. Oxidation of 1 with aqueous H2O2, elemental sulfur or gray selenium gave the corresponding oxide, sulfide and selenide dichalcogenides [Ph2P(E)NHC6H4CH2NHP(E)Ph-2] (E: O, 2a; S, 2b; Se, 2c), respectively. The reaction of [Ph2PNHC6H4CH2NHPPh2] with PdCl2(cod), PtCl2(cod) and [Cu(MeCN)(4)]PF6 gave the corresponding chelate complexes, PdCl(2)1, PtCl(2)1 and [Cu(1)(2)]PF6. The new compounds were fully characterized by NMR, IR spectroscopy and elemental analysis. The catalytic activity of the Pd(II) complex was tested in the Suzuki coupling and Heck reactions. The Pd(II) complex catalyzes the Suzuki coupling and Heck reaction, affording biphenyls and stilbenes respectively, in good yields. Copyright (c) 2008 John Wiley & Sons, Ltd.