Search results for "Phosphines"
showing 10 items of 59 documents
Ligands P-stéréogéniques dérivés du calix[4]arène. Synthèses et applications en catalyse asymétrique
2010
We were interested in synthesis of P-stereogenic ligands derived from calix[4]arene and in their application in asymmetric catalysis. Mono et diphosphines were prepared on the upper rim of the macrocyle starting from the mono or dianion of the calix[4]arene and chlorophosphines borane or the oxazaphospholidine borane complex. The best selectivity was obtained by reaction of the dianion with the oxazaphospholidine borane complex leading to a bisaminophosphine borane. After acidolysis with HCl giving the corresponding bischlorophosphine and reaction with organolithium reagents, diphosphines diborane were obtained with good yields (40 à 60 %). X-ray structures of the prepared ligands confirmed…
From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13 Cu2 Nanoclusters
2018
A general method, using mixed ligands (here diphosphines and thiolates) is devised to turn an achiral metal cluster, Au13 Cu2 , into an enantiomeric pair by breaking (lowering) the overall molecular symmetry with the ligands. Using an achiral diphosphine, a racemic [Au13 Cu2 (DPPP)3 (SPy)6 ]+ was prepared which crystallizes in centrosymmetric space groups. Using chiral diphosphines, enantioselective synthesis of an optically pure, enantiomeric pair of [Au13 Cu2 ((2r,4r)/(2s,4s)-BDPP)3 (SPy)6 ]+ was achieved in one pot. Their circular dichroism (CD) spectra give perfect mirror images in the range of 250-500 nm with maximum anisotropy factors of 1.2×10-3 . DFT calculations provided good corre…
Enantio- and diastereocontrol in intermolecular cyclopropanation reaction of styrene catalyzed by dirhodium(II) complexes with bulky ortho-metalated …
2004
Enantiomerically pure dirhodium(II) complexes with ortho-metalated p-substituted aryl phosphines have been shown to be enantio- and diastereoselective in the cyclopropanation of styrene by ethyl diazoacetate. Enantioselectivities up to 91% and diastereoselectivities up to 90% are observed for ethyl cis-2-phenylcyclopropanecarboxylate. Estevan Estevan, Francisco, Francisco.Estevan@uv.es ; Lahuerta Peña, Pascual, Pascual.lahuerta@uv.es ; Lloret Fillol, Julio, Julio.Lloret@uv.es ; Sanau Torrecilla, Mercedes, Mercedes.Sanau@uv.es ; Ubeda Picot, M Angeles, Angeles.Ubeda@uv.es ; Vila Gomez, Jaume Llorenc, Jaume.Vila@uv.es
Palladium-catalyzed formation of secondary and tertiary amines from aryl dihalides with air-stable ferrocenyl tri- and diphosphines: Synthesis and X-…
2014
Abstract Robust, air-stable tridentate and bidentate ferrocenylphosphines 1,2-bis(diphenylphosphino)-1′-(diisopropylphosphino)-4-tert-butylferrocene, L5, and 1,1′-bis(diisopropylphosphino)-3,3′-bis(tert-butyl)ferrocene, L9, combined with 1 mol% of [PdCl(η3-C3H5)]2 led to two new catalytic systems which allow the coupling of aniline derivatives with mono- and dihaloarenes to form functionalized diarylamines and triarylamines. The excellent selectivity of the reactions avoids the deleterious dehalogenation of the substrates and products. The X-ray structure characterization of the related complex [PdCl2(L9)] is reported in which ligand L9 in its meso form is significantly distorted.
General route to dissymmetric heteroannular-functionalized ferrocenyl 1,2-diphosphines: selective synthesis and characterization of a new class of tr…
2006
Several monosubstituted-cyclopentadienyl anions (A-Li) and [1,2-bis(diphenylphosphino)-4-tert-butylcyclopentadienyl]lithium (B-Li) react with FeCl2 to afford a novel class of multidentate ferroceny...
Gold(I) Complexes Nuclearity in Constrained Ferrocenyl Diphosphines: Dramatic Effect in Gold‐Catalyzed Enyne Cycloisomerization
2020
International audience; Di-tert-butylated-bis(phosphino)ferrocene ligands bearing phosphino substituents R (R=phenyl, cyclohexyl, isopropyl, mesityl, or furyl) allow tuning the selective formation of Au(I) halide complexes. Thus, dinuclear linear twocoordinate, but also rare mononuclear trigonal three-coordinate and tetrahedral four-coordinate complexes were formed upon tuning of the conditions. Both Au(I) chloride and rarer Au(I) iodide complexes were synthesized, and their X-ray diffraction analysis are reported. The significance of the control of structure and nuclearity in Au(I) complexes is further illustrated herein by its strong effect on the efficiency and selectivity of gold-cataly…
Label swapper device for spectral amplitude coded optical packet networks monolithically integrated on InP
2011
In this paper the design, fabrication and experimental characterization of an spectral amplitude coded (SAC) optical label swapper monolithically integrated on Indium Phosphide (InP) is presented. The device has a footprint of 4.8x1.5 mm 2 and is able to perform label swapping operations required in SAC at a speed of 155 Mbps. The device was manufactured in InP using a multiple purpose generic integration scheme. Compared to previous SAC label swapper demonstrations, using discrete component assembly, this label swapper chip operates two order of magnitudes faster. © 2011 Optical Society of America.
The Important Role of the Nuclearity, Rigidity, and Solubility of Phosphane Ligands in the Biological Activity of Gold(I) Complexes
2018
A series of 4-ethynylaniline gold(I) complexes containing monophosphane (1,3,5-triaza-7-phosphaadamantane (pta; 2), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (3), and PR3 , with R=naphthyl (4), phenyl (5), and ethyl (6)) and diphosphane (bis(diphenylphosphino)acetylene (dppa; 7), trans-1,2-bis(diphenylphosphino)ethene (dppet; 8), 1,2-bis(diphenylphosphino)ethane (dppe; 9), and 1,3-bis(diphenylphosphino)propane (dppp; 10)) ligands have been synthesized and their efficiency against tumor cells evaluated. The cytotoxicity of complexes 2-10 was evaluated in human colorectal (HCT116) and ovarian (A2780) carcinoma as well as in normal human fibroblasts. All the complexes showed a hi…
Progress in palladium-based catalytic systems for the sustainable synthesis of annulated heterocycles: a focus on indole backbones
2012
BIOVERT+LDJ; A survey highlighting the most recent palladium catalytic systems produced and their performances for progress in direct synthesis of indole backbones by heterocarbocyclization of reactive substrates is provided. The discussion is developed in relation with the principles of sustainable chemistry concerning atom and mass economy. In this respect, the general convergent character of the syntheses is of particular interest (one-pot, domino, cascade or tandem reactions), and the substrates accessibility and reactivity, together with the final waste production, are also important. This critical review clearly indicates that the development of ligand chemistry, mainly phosphines and…
Resolution of β-aminophosphines with chiral cyclopalladated complexes
2005
Abstract Resolution of the racemic chiral β-aminophosphines Ph 2 PCH 2 CH(Ph)NH(Ar) ( L 1 for Ar = C 6 H 5 and L 2 for Ar = 2,6-C 6 H 3 i Pr 2 ) has been investigated by use of different cyclopalladated complexes as chiral agents. The resulting complexes afford diastereomeric adducts in a 1:1 ratio. After successive crystallizations from ethanol, a d.e. of 98% was achieved for one aminophosphine palladium complex, while no significant d.e. was obtained after crystallizations from chlorinated solvents. The X-ray structure analysis has pointed out intermolecular hydrogen interactions N–H⋯Cl between the P,N ligand and the chloride ion, which are responsible for the formation and stabilization …