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An efficient and highly enantioselective (up to 95% ee) Cu-catalyzed method for asymmetric conjugate addition (ACA) of alkylzinc reagents to acyclic disubstituted nitroalkenes is presented. Reactions are typically effected at ambient temperature in the presence of 2 mol % chiral dipeptide phosphine and 1 mol % (CuOTf)2·C6H6. Nitroalkenes bearing aromatic as well as aliphatic substituents readily undergo asymmetric additions.

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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 crystal structure of the compound [NiBr2(C31H32NP)] (I) was analyzed. The compound is an example of nickel-iminophosphine N,P chelate with the nickel atom in tetrahedral coordination. The nickel coordination is distorted due to the N-Ni-P chelate bite angle of 91.07. In its analouge compound the Ni-N and Ni-P distances were observed to be greater than in a series of related complexes with square planar nickel.

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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 invention relates to a quinoline chiral wicked zuo NNP-type ligand and its synthetic method and application, the ligand has the general formula 1 or 2 the structure: at the time of preparation, in order to Fmoc – Cl and chiral amino acid compound 3 as the starting material, through multi-step by the reaction of the chiral ligand 1, chiral ligand 2. And can be applied to the catalytic synthesis of chiral fluorinated beta ketoester and for palladium-catalyzed asymmetric allylic substitution reaction synthesizing chiral c dione derivatives and chiral c protonic acids derivatives. Compared with the prior art, the invention mild reaction conditions, is easy to operate, repeatability is good, can be a large number of preparation, the prepared catalyst used in the beta ketoester fluorination reaction and palladium-catalyzed asymmetric allylic substitution reaction, has higher ee value and yield. (by machine translation)

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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 novel way to counterbalance the drawbacks and advantages of photopolymerization and redox polymerization is proposed. Photoinitiating systems based on charge transfer complexes (CTC) between a phosphine and an iodonium salt as well as an amine and iodonium salt are checked for the free radical polymerization of methacrylates. Polymer materials as thick as 8.5 cm can be produced under air upon exposure to a LED at 405 nm using an amine/phosphine/iodonium three-component photoinitiating system. When combined with benzoyl peroxide (BPO), these systems are active in photoinduced redox polymerization; i.e., the CTC is used to absorb the light and generates initiating radicals and the amine/BPO couple allows a redox polymerization. Therefore, a fast/slow time control of the radical reaction is feasible under air, and an excellent monomer conversion is obtained both at the top layer and in the core of the sample. The efficiency of this photoactivated redox system is assessed in terms of monomer conversion (followed by FTIR and RAMAN analysis) and time control. The chemical mechanisms are studied using UV-vis absorption spectroscopy, steady-state photolysis, 31P NMR, and ESR-spin trapping experiments.

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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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Rhodium-catalyzed hydroformylation of 1-octene in the presence of different phosphine and phosphine oxide ligands has been investigated. The molecular structure of new phosphine ligand, fluorenylidine methyl phenyl diphenylphosphine, was determined by single-crystal X-ray crystallography. Parameters such as different ligands, molar ratio of ligand to rhodium complex, ratio of olefin to rhodium complex, pressure of CO: H2 mixture, and time of the reaction were studied. The linear aldehyde was the main product when the phosphine ligands were used as auxiliary ligands while the selectivity was changed to the branched products when the related phosphine oxide ligands were used. Under optimized reaction conditions, in the presence of [Rh(acac)(CO)(Ph3P)]-di(1-naphthyl)phenyl phosphine oxide, conversion of 1-octene reached 97% with 87% selectivity of branched aldehyde.

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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 three-step synthesis of new mixed P/N/N?/O-donor ligands C 6H3(OH){2-NHC(O)CH2NCHC6H 4PPh2}(4-CH3) 3a·HH and C 6H4(OH){3-NHC(O)CH2NCHC6H 4PPh2} 3b·HH, by Schiff base condensation of the 1 amines C6H3(OH){2-NHC(O)CH2NH 2}(4-CH3) 2a or C6H4(OH){3-NHC(O) CH2NH2} 2b with C6H4(CHO)(2-PPh 2) in refluxing EtOH, is described. Reaction of 1 equiv. of 3a·HH or 3b·HH with MCl2(cod) (M = Pt, Pd; cod = cycloocta-1,5-diene) affords the kappa2-PN-chelate complexes MCl2(3a·HH) (M = Pd 4a; M = Pt 4b) and MCl 2(3b·HH) (M = Pt 4c). The dichlorometal(II) complexes 4d and 4e, bearing instead a pendant 4-phenolic group, were similarly prepared (in >90% yield). Chloro-bridge cleavage of [Pd(mu-Cl)(eta3-C 3H5)]2 with 3a·HH or 3b·HH gave the monocationic kappa2-PN-chelate complexes [Pd(eta3- C3H5)(3a·HH)]Cl 5a or [Pd(eta3-C 3H5)(3b·HH)]Cl 5b, respectively. Elimination of cod, and single CH3 protonation, from Pt(CH3) 2(cod) upon reaction with 1 equiv. of 3a·HH or 3b·HH in C7H8 at room temperature afforded the neutral complexes C6H3(OH){2-NC(O)CH2NCHC6H 4PPh2Pt(CH3)}(4-CH3) 6a and C 6H4(OH){3-NC(O)CH2NCHC6H 4PPh2Pt(CH3)} 6b, respectively bearing a monoanionic (3a·H- or 3b·H-) kappa3-PNN?-tridentate ligand. Amide and phenol deprotonation were readily achieved, using KOtBu as base, to give high yields of the kappa4-PNN?O-tetradentate complexes C6H 3(O){2-NC(O)CH2NCHC6H4PPh 2Pd}(4-CH3) 7a and C6H3(O){2-NC(O) CH2NCHC6H4PPh2Pt}(4-CH3) 7b bearing the dianionic ligand 3a2-. All new compounds have been characterised by multinuclear NMR, FTIR, mass spectroscopy and microanalysis. Single crystal X-ray studies have been performed on compounds 1b·1.5CH2Cl2, 3b·HH·0.5Et 2O, 6b·CHCl3 and 7b·0.5Et2O.

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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 complexes Rh(COD)(NN)Cl (NN=2,2?-bipyridine or 1,10-phenanthroline derivatives) react with o-(diphenylphosphino)benzaldehyde (PCHO) (Rh-PCHO=1:1) to give acylhydride [Rh(Cl)(H)(PCO)(NN)] species. When this reaction is performed in the presence of SnCl2, neutral trichlorostannate compounds with phosphorus trans to tin [Rh(SnCl3)(H)(PCO)(NN)] are obtained and the complexes containing bipyridine derivatives undergo deinsertion of SnCl2 from the Rh-Cl bond in solution. The oxidative addition of PCHO to Rh(COD)(NN)Cl in the presence of PPh3 gives cationic species [Rh(H)(PCO)(PPh3)(NN)]+ containing mutually trans phosphorus atoms. The reaction of Rh(COD)(NN)Cl with PCHO (Rh-PCHO=1:2) affords cationic complexes [Rh(H)(PCO)(PCHO)(NN)]+ where PCHO behaves as P-monodentate ligand and contains a free aldehyde group. The aldehyde group in [Rh(H)(PCO)(PCHO)(bipy)]+, may undergo the insertion reaction into the Rh-H bond to give the hydroxyalkyl derivative [Rh(PCO)(PCHOH)(bipy)]+.

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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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Catalyst-substrate hydrogen bonds in artificial catalysts usually occur in aprotic solvents, but not in protic solvents, in contrast to enzymatic catalysis. We report a case in which ligand-substrate hydrogen-bonding interactions cooperate with a transition-metal center in alcoholic solvents for enantioselective catalysis. Copper(I) complexes with prolinol-based hydroxy amino phosphane chiral ligands catalytically promoted the direct alkynylation of aldehydes with terminal alkynes in alcoholic solvents to afford nonracemic secondary propargylic alcohols with high enantioselectivities. Quantum-mechanical calculations of enantiodiscriminating transition states show the occurrence of a nonclassical sp3-C-H…O hydrogen bond as a secondary interaction between the ligand and substrate, which results in highly directional catalyst-substrate two-point hydrogen bonding. Efficient enantioselective direct carbonyl addition of terminal alkynes is achieved through ligand-substrate two-point hydrogen bonds consisting of O-H…O and sp3-C-H…O interactions that cooperate with copper in alcoholic solvents (see picture). 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 new flexible C1-symmetric tridentate ligand (S)-N-(2-(tert-butylsulfinyl)benzyl)-1-(pyridin-2-yl)methanamine sulfoxide (L1) was successfully prepared and utilized as a chiral ligand for Ir(I)-catalyzed ATH (asymmetric transfer hydrogenation) reactions. Without any cooperation of other chiral center, encouraging ee and conversion values have been achieved, which provide us a better understanding on these types of ligands and a new strategy to develop new high-efficiency chiral catalysts for asymmetric reaction.

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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 Ugi multi-component reaction is employed for the efficient synthesis of chiral ligands starting from amino acids and aryl aldehydes bearing a Lewis-base functionality. Tests on the products as ligands for enantioselective transition metal catalysis gave promising results in the palladium-catalyzed allylic substitution with e.e. values up to 81%.

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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