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Polyhedral oligomeric silsesquioxanes (POSS) linked ligand of the general formula (I): L [(R1a)n-1(SiO1,5)n R2a ]k [(R1b)n-1SiO1,5)n R2b ]| [(R1C)n-1SiO1,5)n R2c ]m in which (R1a,b,c)n-1(SiO1,5)n is a polyhedral oligomeric silsesquioxanes (POSS) with n = 4, 6, 8,10, 12, 14, 16 or 18 and R1a, R1b,R1c is each independently selected from the group consisting of same or different branched or linear C1-C20 alkyl chains, cyclo alkyl, C1-C20 alkoxy, aryl, aryloxy, heteroaryl and arylalkyl groups, k, l, m is 0 or 1 provided that k+l+m ? 1, R2a, R2b, R2c is a spacer that binds the polyhedral oligomeric silsesquioxane (POSS) to the ligand L and ligand L is an uncharged electron donor.

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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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We report here the remarkable properties of PAd3, a crystalline air-stable solid accessible through a scalable SN1 reaction. Spectroscopic data reveal that PAd3, benefiting from the polarizability inherent to large hydrocarbyl groups, exhibits unexpected electron releasing character that exceeds other alkylphosphines and falls within a range dominated by N-heterocyclic carbenes. Dramatic effects in catalysis are also enabled by PAd3 during Suzuki-Miyaura cross-coupling of chloro(hetero)arenes (40 examples) at low Pd loading, including the late-stage functionalization of commercial drugs. Exceptional space-time yields are demonstrated for the syntheses of industrial precursors to valsartan and boscalid from chloroarenes with ?2 × 104 turnovers in 10 min.

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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

Extended knowledge of Di(adamantan-1-yl)phosphine

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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.131211-27-3, Name is Di(adamantan-1-yl)phosphine, molecular formula is C20H31P. In a Article,once mentioned of 131211-27-3, Recommanded Product: Di(adamantan-1-yl)phosphine

We report copper(I)-catalyzed enantio- and diastereodivergent borylative coupling of styrenes and imines to produce enantiomerically-enriched alpha,beta-dibranched gamma-boryl amine derivatives. Each of the four possible stereoisomers of the products, derived from the two contiguous stereocenters, was selectively accessible by choosing a proper chiral ligand for the copper catalyst. This method, which combines catalyst-controlled stereodivergency and constitutional divergency derived from the lynchpin motif (i.e., the C?B bond), offers a strategy for addressing the construction of molecular structural diversity concomitant with precise chirality control.

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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 dicationic Ni(II) complex [Ni(Pigiphos)(THF)](ClO4)2, [1](ClO4)2 ((R)-(S)-Pigiphos = bis-{(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}cyclohexylphosphine), catalyzes the addition of bulky aliphatic secondary phosphines to methaacrylonitrile. This hydrophosphination reaction reaches TON = 900 and enantioselectivities up to 94%. A catalytic cycle involving 1,4-conjugate addition of R2PH to methacrylonitrile is supported by the isolation and characterization of a catalytically active N-coordinated, methacrylonitrile Ni complex. 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

Discovery of Di(adamantan-1-yl)phosphine

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A series of sterically bulky diphosphines have been prepared, including P2 = trans-1,2-bis[(di-tert-butylphosphino)methyl]cyclohexane (4), (2-methylenepropane-1,3-diyl)bis(di-tert-butylphosphine) (5), bis[(di-tert-butylphosphino)methyl]dimethylsilane (6), and cis- and trans-11,12-bis[(di-tert-butylphosphino)methyl]-9,10-dihydro-9,10-ethanoanthracene (10 and 11). The corresponding palladium complexes of these ligands, P2Pd(CF3CO2)2, have been synthesized and characterized. The solid-state structures of [Pd(4)(CF3CO2)2], [Pd(5)(CF3CO2)2], [Pd(6)(CF3CO2)2], and [Pd(11)(CF3CO2)2] were obtained by single-crystal X-ray diffraction and confirm the bidentate binding mode of the ligand and a square-planar coordination geometry with a minor distortion from the ideal. The diphosphines in combination with Pd(OAc)2 have been applied in the hydroxycarbonylation of a mixture of pentenoic acid isomers to produce adipic acid with high selectivity (in several cases >95%). The (regio)selectivity of the hydroxycarbonylation reaction is highly dependent on the P2 diphosphine ligand structure, particularly the steric bulk of the substituents on the diphosphine donor and the P-Pd-P bite angle in the complexes, with respectively tertiary alkyl phosphine substituents (tert-butyl, adamantyl) and a C4 backbone P-Pd-P bite angle >100 being the common features of highly adipic acid selective systems. It is suggested that the regioselectivity of hydroxycarbonylation becomes largely driven by the chelation of the carboxylic acid functionality of pentenoic acid substrates, when smaller size P substituents and/or when P2 ligands with smaller bite angles (<100) are applied. I hope this article can help some friends in scientific research. I am very proud of our efforts over the past few months and hope to 131211-27-3, help many people in the next few years., Application of 131211-27-3

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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131211-27-3, Name is Di(adamantan-1-yl)phosphine, molecular formula is C20H31P, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 131211-27-3, Recommanded Product: Di(adamantan-1-yl)phosphine

Acylphosphines of the type (1-Ad)nP3-n (n=1,2; R=t-Bu, 1-Ad, Ph) were synthesized via the reaction of 1-AdPH2 or (1-Ad)2PH with the corresponding carboxylic acid chlorides/NEt3.The reaction of 1-AdPH2 with phtaloyl dichloride/NEt3 led to the five-membered heterocycle 4.In the case of n=1, R=1-Ad the monosubstitution product 1-AdP(H)C(:O)(1-Ad) 1b was also observed. 1-AdP(H)C(:O)Ph 1e was selectively formed when 1-AdPH2 was allowed to react with PhC(:O)Cl/K2CO3, whereas the remaining PH-proton in 1e could be substituted by C(:O)t-Bu in its reaction with t-BuC(:O)Cl/NEt3 to give 2d.The action of trifluoroacetic acid anhydride on 1-AdPH2 or (1-Ad)2PH led to the trifluoroacetyl phosphines 2c and 3c.The reaction of 1-AdP2 2a with aqueous H2O2 or elemental sulfur furnished the corresponding chalcogenides 5 and 6, with a large excess of methyl iodide <1-AdPMe3>I 7 was formed.The carbonyl complexes (L)M(CO)n (L=2a; M=Ni, n=3:8; M=Fe, n=4:9) were obtained upon reaction of 2a with Ni(CO)4 and Fe2(CO)9, respectively.Tris-1-adamantoylphosphine 10 was formed as a by-product in the reaction of P(SiMe3)3 with 1-AdC(:O)Cl and was converted to the chalcogenides <(1-AdC(:O)>3P(:X) (X=O: 13; X=S: 14). Key words: Acyl phosphines; 1-adamantyl phosphorus compounds; NMR.

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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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Phosphenium compounds with the general formula I: in which R1, R2, R3 and R4 are identical or different and represent a linear or branched C1-C6-alkyl radical, which can optionally be substituted, or R1 and R2 and/or R3 and R4 are bonded to one another with the formation of a ring, R5 and R6 stand for a saturated or unsaturated and linear or branched alkyl group, alkenyl group or aryl group, which can have suitable substituents, even heteroatoms as substituents, or a heteroatom-comprising hydrocarbon group, which can have suitable substituents, and the R5 and R6 radicals can form a ring which can be 4- to 20-membered, saturated or unsaturated and alicyclic or heteroalicyclic and can exhibit suitable substituents, X? represents an anion, a process for the preparation thereof, and also the use of these compounds in metal complexes which can be used as catalysts in organic synthesis, are claimed.

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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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131211-27-3, Name is Di(adamantan-1-yl)phosphine, molecular formula is C20H31P, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 131211-27-3, Quality Control of: Di(adamantan-1-yl)phosphine

The invention relates to a process for the synthesis of aryl hydrazinesof formula I or a salt thereof, which process comprises subjecting an arene of formula II to a coupling reaction with hydrazine or a derivative thereof, wherein the coupling reaction is conducted in the presence of a catalyst comprising palladium and a diphosphine ligand, wherein the phosphorus atoms are connected through two, three, four, or five atoms selected from car- bon, nitrogen, oxygen or iron, and in which the non-connecting phosphorus substituents are C1- C 10-alkyl or C3-C10-cycloalkyl, wherein the amount of Pd used is up to 0.5 mol-% relative to the amount of arene of formula II; and a base.

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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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131211-27-3, Name is Di(adamantan-1-yl)phosphine, molecular formula is C20H31P, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 131211-27-3, category: chiral-phosphine-ligands

The present invention provides a catalyst system capable of catalyzing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining: a) a metal of Group VIB or Group VIIIB or a compound thereof, b) a bidentate phosphine, arsine or stibine ligand, and c) an acid, wherein the ligand is present in at least a 2:1 molar excess compared to the metal or the metal in the metal compound, and that the acid is present in at least a 2:1 molar excess compared to the ligand, a process for the carbonylation of an ethylenically unsaturated compound, a reaction medium, and use of the system.

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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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Chiral gold(I) catalysts have been designed based on a modified JohnPhos ligand with a distal C2-2,5-diarylpyrrolidine that creates a tight binding cavity. The C2-chiral element is close to where the C-C bond formation takes place in cyclizations of 1,6-enynes. These chiral mononuclear catalysts have been applied for the enantioselective 5-exo-dig and 6-endo-dig cyclization of different 1,6-enynes as well as in the first enantioselective total synthesis of three members of the carexane family of natural products. Opposite enantioselectivities have been achieved in seemingly analogous reactions of 1,6-enynes, which result from different chiral folding of the substrates based on attractive aryl-aryl interactions.

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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