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Direct aromatic C – H bond activation in the (Sa)-BINOL-derived phosphite (Sa)-HL afforded the dimeric cyclopalladated complex (Sa,Sa)-{Pd(eta2-L)(mu-Cl)}2 (2) which is the first optically active PC-palladacycle bearing a phosphorus atom in an axially chiral environment. ortho-Palladated structure of dimer 2 was confirmed by spectral (1H and 31P NMR) examination of its mononuclear derivatives and by X-ray diffraction analysis of the phosphine adduct (eta2-L)PdCl(PPh3) (4). The enantiomeric purity of the starting ligand remained unchanged in the PC-palladacycle under the thermal conditions used for the cyclopalladation (?110C); this fact was confirmed by the 31P NMR spectroscopy after chiral derivatization in situ of dimer (Sa,Sa)-2 with the (RC)-valinate chiral auxiliary (Val). trans(N,C)-Configuration of the valinate complex (eta2-L)Pd(Val) (5) was established by H NMR and supported by DFT calculations. The chirality transfer in the new PC-palladacycle was discussed on the basis of X-ray diffraction data for the phosphine adduct rac-4 and DFT calculations performed for both phosphine and valinate mononuclear derivatives.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Diastereoselective syntheses of the unusual dimers, 4-heptyl-2-(2?- hydroxy-binaphthyl)hydrogen phosphonate (5) and the cyclohexyl analogue (7), are achieved by hydrolysis of 4-(3,5-dioxa-4-phosphacyclohepta[2,1-alpha;3,4- alpha?]dinaphthalene-4-yloxy)heptane (4) and the cyclohexane analogue (6), respectively. Two out of eight possible pairs of monomers units are involved in the stereoselective formation of the dimer 5a of configuration BINOLR-PS:BINOLR-PS: this is determined by X-ray crystallographic data, which reveal a centrosymmetric, 18-membered ring structure with Ci symmetry, consisting of two monomers strongly hydrogen-bonded between the oxygen of P=O units and hydroxyl hydrogen atoms. Mass spectrometric, melting point, and thermal decomposition point data, as well as NMR data, support the presence of strong, quasi-covalent hydrogen bonds. Computational analysis suggests that the diastereoselectivity is controlled by molecularly constrained geometry of the monomer. Compound 7, although not characterized crystallographically, appears to be analogous to 5.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.155613-52-8, Name is (R)-1,1-Binaphthyl-2,2-diyl phosphorochloridate, molecular formula is C20H12ClO2P. In a Article,once mentioned of 155613-52-8, Application In Synthesis of (R)-1,1-Binaphthyl-2,2-diyl phosphorochloridate

Effective and modular synthetic approaches toward phosphine-phosphite ligands and phosphine-phosphonite ligands featuring a diphenyl ether backbone have been developed. The phosphine-phosphite ligands are obtained by a two-step protocol from 2-bromo-2?-methoxydiphenyl ether. The phosphine-phosphonite ligands are prepared in a four-step synthetic protocol that involves a novel, unsymmetrical diphenyl ether derived phosphine-phosphorusdiamide as key building block. Structural studies on PtII complexes with either phosphine-phosphite or phosphine-phosphonite ligands indicate strict cis coordination for these ligand systems. High-pressure NMR spectroscopy studies of Rh complexes under syngas indicate the presence of two ea isomers for Rh(H)(CO)2(PP). The existence of this mixture is further supported by high-pressure IR spectroscopy studies. In order to benchmark the activity and selectivity of these novel, wide-bite-angle, mixed-donor ligands, they were screened in Pd-catalyzed asymmetric allylic alkylation as well as Rh-catalyzed hydrogenation and hydroformylation reactions. The ligands give 100-% conversion and low-to-moderate enantioselectivity in the allylic alkylation of 1,3-diphenyl-2-propenyl acetate and cyclohexyl-2-enyl acetate with dimethyl malonate. In the hydroformylation of styrene, good conversion and regioselectivities are achieved but only moderate enantioselectivity. The ligands give good conversions in asymmetric hydrogenation of typical substrates, with good-to-excellent enantioselectivities of up to 97-% depending on the substrate. The design of two subclasses of chiral, mixed-donor diphosphorus ligands with a diphenylether backbone is described. Both phosphine-phosphonite and phosphine-phosphite derivatives are accessible. Coordination to PtII and RhI is described, and high-pressure spectroscopy under syngas provides information on coordination geometry. The chiral ligand systems are benchmarked in Pd-catalyzed allylic alkylation and Rh-catalyzed hydrogenation and hydroformylation.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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An Ir(P,alkene) complex catalyzes the enantioselective allylic etherification of unactivated secondary allylic alcohols. Useful levels of enantioselectivity and yield were achieved with this operationally easy and robust protocol. Initial kinetic studies indicate a significant rate difference for the substrate enantiomers, allowing for a resolution process. cod=1,5-cyclooctadiene Copyright

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A series of the new chiral BINOL-based phosphite P,N-hybrid ligands was prepared. The coordination behavior of all the ligands was studied and the neutral complexes [Rh(CO)Cl(P N)] were synthesized in order to characterize a degree of the electronic non-symmetry of donating centers. Also the neutral and cationic complexes cis-[PdCl2(eta2-P N=)], cis-[PdCl2(eta1-P N=)2], cis-[PdCl(eta2-P N=) (eta1-P N=)]+Cl-,[Pd(allyl)(eta2-P N=)]+X- (X- = Cl-, BF4-) were obtained and characterized. The new P,N-hybrid ligands gave up to 81% ee in the enantioselective Pd-catalyzed alkylation of 3-penten-2-yl carbonate by dimethyl malonate and up to 60% ee in the Rh-catalyzed hydrosilylation of acetophenone and acetylferrocene by diphenylsilane.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 155613-52-8, Name is (R)-1,1-Binaphthyl-2,2-diyl phosphorochloridate, molecular formula is C20H12ClO2P. In a Article,once mentioned of 155613-52-8, Application In Synthesis of (R)-1,1-Binaphthyl-2,2-diyl phosphorochloridate

For the first time enantiomerically pure phosphine-or phosphite-substituted 1,1-alkyl-3,3?-bi-indolizines were obtained. In situ prepared rhodium complexes of these compounds were tested in hydroformylation of styrene and methylstyrene.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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New unsymmetrical diphosphazanes of the type X2PN(Pri)PYY’ are prepared and converted into their mono- and di-oxides or sulfides.These can function as heterofunctional ligands through P,S,N or O donor sites.These compounds have been characterized by NMR spectroscopic studies.Variable temeprature 31P<1H> NMR measurements on some of these compounds reveal the presence of different types of conformers in solution.Single crystal X-ray diffraction studies have been carried out for Ph2(S)N(Pri)PPh(N2C3HMe2-3,5) (2g) and Ph2P(O)N(Pri)P(O)Ph(OC5H4N-2) (5h). Key words: Unsymmetrical diphosphazanes; their monosulfides, monoxides and dioxides; syntheses; NMR spectra; crystal structures.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The regioisomeric composition of the adducts of unsymmetrical oxiranes with achiral and chiral phosphorochloridites was studied. Factors allowing enantiomeric assessment of chiral oxiranes with the aid of chiral derivatizing organophosphorus reagents were revealed.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Although phosphonous acid ligands have recently become of interest for use in transition metal complex catalysts for organic reactions such as alkene hydroformylations, the factors that affect the steric and electronic properties of these ligands have not been studied in detail. To gain insight into the electronic and steric properties of phosphonous acid ligands, we have prepared tungsten(0) pentacarbonyl complexes with chlorophosphite ligands derived from either 2,2?-biphenol or (±)-1,1?-bi-2-naphthol and have then hydrolyzed the coordinated ligands to generate tungsten(0) pentacarbonyl complexes with the corresponding phosphonous acid ligands. NMR measurements of the W-P coupling constants demonstrate that changing the biaryl groups from biphenyl to binaphthyl does not affect the electron-donor ability of the ligand, whereas changing the third substituent from chloro to oxo has a significant effect. Estimation of cone angles of the ligands from X-ray crystallographic data have shown that neither changing the biaryl group nor changing the third substituent have a significant effect on their cone angles. Further, these studies have identified important intra- and intermolecular interactions that favor certain ligand conformations. The data could be useful for the development of catalytic structure-activity relationships that could be used in the rational design of catalysts. Steric and electronic properties of chlorophosphite ligands derived from 2,2?-biphenol or (±)-1, 1?-bi-2-naphthol and their corresponding phosphonous acid ligands in tungsten(0) pentacarbonyl have been studied by using multinuclear NMR spectroscopy and X-ray crystallography. The identity of the biaryl group does not affect either the steric or the electronic properties of the ligands. Copyright

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Organic chromophores with charge asymmetry may exhibit significant second-order nonlinear optical (NLO) properties. Metal complexes have been used as the donor, the acceptor, or as the bridge in some of these chromophores. Metal complexes may also be useful in dipolar chromophore orientation and in the building of large molecular structures, but this approach remains largely unexplored. We herein report the syntheses and characterization of a novel class of phosphite-containing chromophores, O2N-1-C6H 4-4-CH=N-1-C6H4-4-OP(OC6H 4)2 (2) and O2N-1-C6H 4-4-X=N-1-C6H4-4-OP(OC10H 6)2 [X = CH (3), N (4)], and their transition-metal complexes, cis-Mo(CO)4(2)2 (5), PdCl2(2) 2 (6), and cis-Mo(CO)4(3)2 (7). The X-ray crystal structures of 2 and 5 show that coordination of the phosphite ligand to the metal atom does not alter the conformation of the chromophore. Hyper-Rayleigh scattering (HRS) measurements of the compounds in 1,4-dioxane at 1064 nm indicate that phosphite functionalization causes a small decrease in the I values of the Schiff-base chromophores {I [esu]: 47aA – a10-30 (1), 25aA – a10-30 (2), 30aA – a10-30 (3} and no change in the I value of the azo chromophore {I [esu]: 62aA – a10 -30 (4)}. The larger I values of the cis-Mo(CO) 4L2 complexes {I [esu]: 38aA – a10-30 (5), 41aA – a10-30 (7)} as compared to those of the ligands (2 and 3) are consistent with the 90orientation of two chromophores in the complexes. A novel class of phosphite-containing chromophores, O2N-1-C6H 4-4-CH=N-1-C6H4-4-OP(OC6H 4)2 (2) and O2N-1-C6H 4-4-X=N-1-C6H4-4-OP(OC10H 6)2 [X = CH (3), N (4)], and their transition-metal complexes, cis-Mo(CO)4(2)2 (5), PdCl2(2) 2 (6), and cis-Mo(CO)4(3)2 (7) were synthesized and fully characterized. Second-order NLO properties of the ligands and complexes were investigated by HRS measurements. Copyright

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate