13,821 research outputs found
P-Stereogenic monophosphines with the 2-p-terphenylyl and 1-pyrenyl substituents. Application to Pd and Ru asymmetric catalysis
tThe synthesis of five optically pure P-stereogenic monophosphines of the type PPhArR (Ar = 2-p-terphenylyl (a), 1-pyrenyl (b); R = OMe, Me, i-Pr) is described. The ligands were fully characterisedand the absolute configurations of PPh(1-pyrenyl)R (3b and 5b; R = OMe and Me respectively) wereconfirmed by X-ray diffraction. The complexation of the monophosphines to Pd and Ru organometal-lic units yielded the neutral complexes [PdCl( 3-2-Me-allyl)P] (10-12) and [RuCl2( 6-p-cymene)P](16-18). Complete characterisation, including the crystal structure determination of [RuCl2( 6-p-cymene)(PMePh(2-p-terphenyl))] (17a) is provided. Neutral palladium complexes appeared as mixturesof two diastereomers in solution according to NMR. The synthesis and characterisation of four cationic[Pd( 3-2-Me-allyl)(P)2]PF6(13 and 14) is also described. The application of neutral Pd complexes tocatalytic styrene hydrovinylation afforded moderate conversions, high chemoselectivities (>92%) to 3-phenyl-1-butene and up to 43% ee with precursor 12a. Cationic Pd complexes were tested as catalyticprecursors in allylic substitution of rac-3-acetoxy-1,3-diphenyl-1-propene (rac-I), with the anion ofdimethylmalonate and benzylamine as nucleophiles, obtaining full conversions and up to 80% ee in alkyl-ation and 60% ee in amination with precursor 13a. Finally, ruthenium complexes were used as catalyticprecursors in transfer hydrogenation of acetophenone, with complete conversions after several hoursbut low enantioselectivities
Cyclopalladated Compounds with Polyhalogenated Benzylphosphanes for the Mizoroki-Heck Reaction
Nine partially halogenated benzylphosphanes ArXCH2PR2 (ArX = 3,6-dichlorophenyl, 3,6- difluorophenyl and 3,4,5-trifluorophenyl; R = Ph, Cy, iPr) have been prepared and reacted with palladium acetate to obtain the cyclometallated dimers [Pd(ÎŒ-OAc)(Îș2-C,P-ArXCH2PR2)]2. The acetate bridge has been exchanged by bromide using lithium bromide and the obtained dimers have been thoroughly characterised. The dimers with the non-halogenated phosphanes PhCH2PR2 (R = Ph, iPr) have also been prepared. Treatment with norbornadiene in the presence of silver tetrafluoroborate has furnished the cationic mononuclear complexes [Pd(Îș2-C,P-ArXCH2PR2)(nbd)]BF4 as stable solids. These complexes and some of the bromide dimers have been used as catalytic precursors in the Mizoroki- Heck reaction between bromobenzene and butyl acrylate. The complexes efficiently catalyse this transformation and important differences of activity are found depending on the ligand. In general, fluorinated phosphanes give more active systems than chlorinated analogues
Ruthenium complexes of P-stereogenic phosphines with a heterocyclic substituent
The synthesis via phosphine-boranes of 13 new optically pure P-stereogenic diarylphosphines P(Het)PhR (Het = 4-dibenzofuranyl (DBF), 4-dibenzothiophenyl (DBT), 4-dibenzothiophenyl-S,S-dioxide (DBTO2) and 1-thianthrenyl (TA); R = OMe, Me, i-Pr, Fc (ferrocenyl)) following the JugĂ©-Stephan method is described. The ligands were designed with the aim of having a heteroatom in a position capable of interacting with a metal upon coordination. The ligands and their precursors have been fully characterised, including the determination of two crystal structures of phosphine-boranes. Ru neutral complexes of the type [RuCl2(η6-arene)(ÎșP-P)] (arene = p-cymene and methyl benzoate) have been prepared and characterised, including three crystal structure determinations. Treatment of solutions of the complexes with TlPF6 allowed the preparation of well-defined cationic complexes [RuCl(η6-arene)(Îș2P,S-P)]PF6 for DBT- and TA-based phosphines. The complexes possess a stereogenic Ru atom and in most of the cases they are present as a single isomer in solution. All the Ru complexes have been used in the asymmetric transfer hydrogenation of acetophenone in refluxing 2-propanol, with good activities and up to 70% ee
Neutral and Cationic Palladium Complexes of P-Stereogenic Phosphanes Bearing a Heterocyclic Substituent
The coordination chemistry of 13 optically pure P âstereogenic diarylmonophosphanes P(Het)PhR [Het = 4âdibenzofuranyl (DBF), 4âdibenzothiophenyl (DBT), 4âdibenzothiophenyl S ,S âdioxide (DBTO2) and 1âthianthrenyl (TA); R = OMe, Me, i Pr, Fc (ferrocenyl)] to Pdâallyl moieties is described. Both neutral [PdCl(η3â(2âmethylallyl)(ÎșP âP )] and cationic [Pd{η3â(2âmethylallyl)(ÎșP âP )2}]PF6 complexes have been prepared. Coordination of the heteroatom of the heterocycle was only possible in the case of TAâbased phosphanes; these furnished complexes of the type [Pd{η3â(2âmethylallyl)(Îș2P,S âP )}]PF6 after chloride abstraction with TlPF6. The crystal structure of the complex [Pd(η3â2âmethylallyl)(Îș2P,S âPPh(OMe)(1âTA)]PF6 is reported. The neutral Pd complexes were found to be highly active in the hydrovinylation of styrene after activation with AgBF4, except for the TAâbased phosphanes. The cationic Pd complexes were evaluated in allylic alkylation and amination with the model substrate rac âtrans â1,3âdiphenylpropâ2âenyl acetate (rac âI ), achieving total conversions and up to 70â% ee
Diphosphorus Ligands Containing a P-Stereogenic Phosphane and a Chiral Phosphite or Phosphorodiamidite - Evaluation in Pd-Catalysed Asymmetric Allylic Substitution Reactions
The synthesis of 14 new optically pure C 1âsymmetric phosphane-phosphinite (1 -4 ), phosphane-phosphite (5 -9 ) and phosphane-phosphorodiamidite (10 -14 ) ligands is reported. The ligands were prepared through the condensation of (2âhydroxyphenyl)phenylphosphanes PPh(2âPhOH)R (R = Me, t Bu and Ph) with chlorodiisopropylphosphane (1 and 2 ), chlorodiphenylphosphane (3 and 4 ), the chlorodioxaphosphepine derived from both enantiomers of 1,1âČâbiâ2ânaphthol (5 -9 ) and the chlorodiazaphosphepine derived from both enantiomers of N ,NâČ âdimethylâ1,1âČâbinaphthylâ2,2âČâdiamine (10 -14 ) in the presence of a base. With these ligands, cationic Pd complexes of the type [Pd(η3âC4H7)(PPâČ)]PF6 (Pd1 -Pd14 ) were obtained and characterised; the crystal structures of Pd1 , Pd2 and Pd13 were obtained. In solution, the complexes are present as mixtures of two diastereomers because of the lack of symmetry of the ligand and the presence of the methallyl group. The Pd complexes catalyse the allylic alkylation with dimethyl malonate and the amination with benzylamine of the model substrate rac â3âacetoxyâ1,3âdiphenylâ1âpropene (I ). For the alkylation, full conversions and good enantioselectivities (up to 96â%âee with Pd14 ) were observed
Highly efficient synthesis of the tricyclic core of Taxol by cascade metathesis
An efficient enantioselective synthesis of the ABC tricyclic core of the anticancer drug Taxol is reported. The key step of this synthesis is a cascade metathesis reaction, which leads in one operation to the required tricycle if appropriate fine-tuning of the dienyne precursor is performed
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