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(diphenylphosphino)-2-(aminomethyl)aniline 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)Ph2] (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, PdCl21, PtCl21 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 © 2009 John Wiley & Sons, Ltd.

[1]  S. Özkar,et al.  Synthesis and characterizations of 3,3′-bis(diphenylphosphinoamine)-2,2′-bipyridine and 3,3′-bis(diphenylphosphinite)-2,2′-bipyridine and their chalcogenides , 2007 .

[2]  P. Dyson,et al.  Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions , 2007 .

[3]  G. Kubas,et al.  Tetrakis(Acetonitrile)Copper(1+) Hexafluorophosphate(1‐) , 2007 .

[4]  A. Shaver,et al.  Cyclic Diolefin Complexes of Platinum and Palladium , 2007 .

[5]  J. Mague,et al.  Aminophosphines derived from morpholine and N-methylpiperazine: synthesis, oxidation reactions and transition metal complexes , 2006 .

[6]  B. Pugin,et al.  The immobilization of rhodium-4-(diphenylphosphino)-2-(diphenylphosphinomethyl)-pyrrolidine (Rh-PPM) complexes : A systematic study , 2006 .

[7]  Z. Dong,et al.  Highly efficient chiral PNNP ligand for asymmetric transfer hydrogenation of aromatic ketones in water , 2006 .

[8]  I. Özdemir,et al.  Use of bis(benzimidazolium)–palladium system as a convenient catalyst for Heck and Suzuki coupling reactions of aryl bromides and chlorides , 2006 .

[9]  I. Beletskaya,et al.  Non-conventional methodologies for transition-metal catalysed carbon–carbon coupling: a critical overview. Part 2: The Suzuki reaction , 2005 .

[10]  E. Zangrando,et al.  [MCl(ligand)]+ Complexes (M = Ni, Pd, Pt) with a P,N,N Terdentate Ligand – Solid State and Solution Structures and Catalytic Activity of the PdII Derivative in the Heck Reaction , 2005 .

[11]  K. K. Hii,et al.  Reversal of aryl bromide reactivity in Pd-catalysed aryl amination reactions promoted by a hemilabile aminophosphine ligand , 2005 .

[12]  Zhaofu Fei,et al.  The chemistry of phosphinoamides and related compounds , 2005 .

[13]  S. E. Large,et al.  A versatile synthesis of phosphine–aminophosphine ligands for asymmetric catalysis , 2005 .

[14]  Duncan M. Tooke,et al.  Chiral bidentate aminophosphine ligands: synthesis, coordination chemistry and asymmetric catalysis. , 2005, Dalton transactions.

[15]  J. Verkade,et al.  Synthesis of N-aryl-aza-crown ethers via Pd-catalyzed amination reactions of aryl chlorides with aza-crown ethers , 2004 .

[16]  V. Farina.  High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview , 2004 .

[17]  A. Slawin,et al.  Preparation and coordination chemistry of p-(xylylenediaminodiphenyl) phosphine , 2004 .

[18]  R. Morris,et al.  Asymmetric Hydrogenation of Ketones Catalyzed by Ruthenium Hydride Complexes of a Beta-aminophosphine Ligand Derived from Norephedrine , 2004 .

[19]  X. Hou,et al.  Synthesis of new chiral benzylically substituted P,N-ligands and their applications in the asymmetric Heck reaction , 2004 .

[20]  F. Agbossou-Niedercorn,et al.  Efficient enantioselective hydrogenation of arylimines using aminophosphine-oxazoline iridium catalysts , 2004 .

[21]  J. Verkade,et al.  Palladium/Proazaphosphatrane‐Catalyzed Amination of Aryl Halides Possessing a Phenol, Alcohol, Acetanilide, Amide or an Enolizable Ketone Functional Group: Efficacy of Lithium Bis(trimethylsilyl)amide as the Base , 2004 .

[22]  A. Slawin,et al.  Synthesis and structure of new phosphines containing P–N bonds , 2004 .

[23]  A. Slawin,et al.  Bis(phosphine) derivatives of diamines , 2004 .

[24]  Yi Pan,et al.  Palladium-catalyzed Suzuki-Miyaura reaction using aminophosphine as ligand , 2003 .

[25]  T. Mino,et al.  A C(aryl)-N(amine) bond atropisomeric aminophosphine: preparation and use as a ligand in a catalytic asymmetric allylic alkylation , 2003 .

[26]  B. R. Steele,et al.  An iminophosphine dendrimeric ligand and its evaluation in the Heck reaction , 2003 .

[27]  R. Scopelliti,et al.  Understanding structure does not always explain reactivity: a phosphinoamide anion reacts as an iminophosphide anion. , 2003, Inorganic chemistry.

[28]  M. Portnoy,et al.  Synthesis of a diverse set of phosphorus ligands on solid support and their screening in the Heck reaction , 2003 .

[29]  J. Steed,et al.  Facile syntheses of new multidentate (phosphino)amines: X-ray structure of 1,4-{(OC)4Mo(Ph2P)2NCH2}2C6H4 , 2002 .

[30]  J. Verkade,et al.  Pd/P(i-BuNCH2CH2)3N: an efficient catalyst for Suzuki cross-coupling of aryl bromides and chlorides with arylboronic acids , 2002 .

[31]  A. Slawin,et al.  Preparation and coordination chemistry of Ph2P(CH2)nNHPiPr2 (n=2, 3) , 2002 .

[32]  G. C. Fu,et al.  Palladium-catalyzed coupling reactions of aryl chlorides. , 2002, Angewandte Chemie.

[33]  A. Slawin,et al.  The preparation and coordination chemistry of phosphorus(III) derivatives of piperazine and homopiperazine , 2002 .

[34]  J. Andrieu,et al.  Synthesis, coordination to Rh(I), and hydroformylation catalysis of new beta-aminophosphines bearing a dangling nitrogen group: an unusual inversion of a Rh-coordinated P center. , 2002, Inorganic chemistry.

[35]  Thomas Schareina,et al.  Combinatorial libraries with P-functionalized aminopyridines: ligands for the preparation of efficient C(aryl)-Cl activation catalysts. , 2002, Angewandte Chemie.

[36]  M. Lemaire,et al.  Aryl-aryl bond formation one century after the discovery of the Ullmann reaction. , 2002, Chemical reviews.

[37]  Xin Li,et al.  The synthesis of a new generation of MAP ligands containing two types of chiral elements for asymmetric catalysis , 2002 .

[38]  D. Cole-Hamilton,et al.  Synthesis of bulky, electron rich hemilabile phosphines and their application in the Suzuki coupling reaction of aryl chlorides , 2001 .

[39]  K. K. Hii,et al.  Advances in the Heck Chemistry of Aryl Bromides and Chlorides , 2001 .

[40]  Yi Wang,et al.  Synthesis of novel N,P chiral ligands for palladium-catalyzed asymmetric allylations: the effect of binaphthyl backbone on the enantioselectivity , 2000 .

[41]  K. K. Hii,et al.  Examination of Ligand Effects in the Heck Arylation Reaction , 2000 .

[42]  I. Beletskaya,et al.  The heck reaction as a sharpening stone of palladium catalysis. , 2000, Chemical reviews.

[43]  Gene-Hsiang Lee,et al.  Palladium(II) Complexes with Phosphorus−Nitrogen Mixed Donors. Efficient Catalysts for the Heck Reaction , 2000 .

[44]  M. Mahon,et al.  Ether functionalised aminophosphines: synthesis and co-ordination chemistry of palladium(II) and platinum(II) complexes , 2000 .

[45]  A. Slawin,et al.  Molybdenum(0), ruthenium(II), palladium(II), platinum(II), copper(I) and gold (I) complexes of a new methoxy functionalised bis(phosphino)amine: synthesis and structure , 2000 .

[46]  M. Widhalm,et al.  Steric hindrance versus asymmetric induction: new PN-ligands for carbon–carbon coupling reactions , 1998 .

[47]  M. Reetz,et al.  Systhesis and Catalytic Activity of Dendritic Diphosphane Metal Complexes , 1997 .

[48]  A. Slawin,et al.  Synthesis, co-ordination chemistry and crystallographic studies of some bis(aminophosphines) , 1997 .

[49]  Chalil Abu-Gnim,et al.  Phosphine oxides as ligands in the hydroformylation reaction , 1996 .

[50]  A. Meijere,et al.  Fine Feathers Make Fine Birds: The Heck Reaction in Modern Garb† , 1995 .

[51]  A. Willis,et al.  Copper(I)-Facilitated Methylation and Cyclic Alkylation of 1,2-Phenylenebis(phosphine) , 1995 .

[52]  J. Clyburne,et al.  Spontaneous formation of a dicoordinate iminophosphine from a tricoordinate triaminophosphine via a tetracoordinate phosphorane , 1993 .

[53]  I. Mathews,et al.  Organometallic chemistry of diphosphazanes. Part 7. Platinum(II), palladium-(o), -(I) and -(II) complexes of RN[P(OPh)2]2(R = Me or Ph) , 1993 .

[54]  M. Doyle,et al.  Efficient palladium catalysts for the copolymerization of carbon monoxide with olefins to produce perfectly alternating polyketones , 1991 .

[55]  G. Daves,et al.  1,2-Additions to heteroatom-substituted olefins by organopalladium reagents , 1989 .

[56]  R. Heck.  Palladium‐Catalyzed Vinylation of Organic Halides , 2005 .

[57]  J. F. White,et al.  Thermal decomposition of bis(phosphine)platinum(II) metallocycles , 1976 .