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Effect of ortho-methyl groups in the benzene rings of the macrocyclic matrix on the chemistry of cavitands with phosphorous amide bridges in the upper rim is studied. The presence of ortho-methyl groups is shown to prevent formation of phosphacavitands of C 4v symmetry and favor formation of macrocyclic systems of C 2v symmetry, enhance solubility of phosphacavitands in organic solvents, hinder oxidation of phospha(III)cavitands and decrease the yield of phospha(V)cavitands, prevent formation of binuclear molybdenum complexes of phosphorous amide cavitands, and favor formation of their tetranuclear analogs.

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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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Porous materials have been of high scientific and technological interest owing to their unique performances in many topical applications related to multiphasic functional systems: gas separation and storage, heterogeneous catalysis, energy conversion, etc. We review herein the synthetic strategies applied for using functionalized adamantane derivatives as polyhedral (mainly tetrahedral, Td-directing) building units of three-dimensional (3-D) porous supramolecular structures and nanomaterials, either purely organic or within metal hybrid frameworks. The resulting materials are currently used in varied heterogeneous (or supported) transition metal catalysis and organocatalysis, including recent high-value asymmetric synthesis. Characterization, synthetic applications and recycling properties of catalytic materials based on adamantane-scaffold are discussed. This review highlights the structuring advantages of variously functionalized-adamantanes to reach high surface area and controlled porosity for exploiting both confinement effects related to modified kinetics (compared to homogeneous) reactions, and pertinent chemo- and enantioselectivity issues.

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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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This chapter describes the rational design and synthesis of semisynthetic lipases by site-directed incorporation of tailor-made peptides on the lipase-lid site to improve its activity, specificity, and enantioselectivity in specific biotransformations. Cysteine was genetically introduced at a particular point of the oligopeptide lid of the enzyme, and cysteine-containing peptides, complementary to the amino acid sequence on the lid site of Geobacillus thermocatenulatus lipase (BTL), were covalently attached on the lid of two different cysteine-BTL variants based on a fast thiol?disulfide exchange ligation followed by desulfurization. The BTL variants were initially immobilized on solid support to introduce the advantages of solid-state chemistry, such as quantitative transformations, easy purification, and recyclability. In the two different immobilized variants BTL-A193C and BTL-L230C, the cysteine was then activated with 2-dipyridyldisulfide to help the disulfide exchange with the peptide, generating the semisynthetic enzyme in high yield. Excellent results of improvement of activity and selectivity were obtained. For example, the peptide?BTL conjugate (at position 193) was 40-fold more active than the corresponding unmodified enzyme for the hydrolysis of per-acetylated thymidine at pH 5, or fourfold in the desymmetrization of dimethyl-3-phenylglutarate at pH 7. The new enzyme also exhibited excellent enantioselectivity in the desymmetrization reaction with enantiomeric excess (ee) of > 99% when compared to that of the unmodified enzyme (ee = 78%).

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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 bidentate phosphoramidite (N-Me-BIPAM) based on Shibasaki’s N-linked BINOL was synthesized. This ligand appears to be highly effective for rhodium-catalyzed asymmetric conjugated addition of arylboronic acids to alpha,beta-unsaturated enones. The reaction of ortho-substituted arylboronic acid with acyclic and cyclic enones provides the corresponding products in good yields and enantioselectivities.

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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 methyl ester of 3-azidotetrafluoropropionic acid, N3-CF2CF2COOMe oxidatively fluorinates P(III), Sb(III) and Te(II) compounds to form the corresponding difluorides in good yield.

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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 of tris-dialkylaminoarsanes on pyrylium salts, giving a new series of pentamethinium salts was extended to the stibanes homologs whereas tris-dimethylaminophosphane yields only phosphonium adducts on the same substrates.

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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 compounds Ph3PSeI2, (Me2N)3PSeI2 and (Et2N)3PSeI2 have been prepared and characterised by 31P-{H} NMR and infrared spectroscopy. Their single crystal structures have also been determined. Interesting variations in d(P-Se) and d(I-I) are noted upon changing R (Ph, Me2N, Et2N). The variation in d(P-Se) for R3PSeI2 compared to the parent tertiary phosphine selenide is also discussed with respect to the degree of retention of phosphorus selenium double-bond character upon co-ordination of I2. The variations in d(P-Se) and d(I-I) are reflected in the infrared and 31P-{H} NMR spectra of the R3PSeI2 compounds when compared to R3PSe (R = Ph, Me2N or Et2N). The P-Se-I geometries for all three compounds are bent [Ph3PSeI2, 106.0(1), (Me2N)3PSeI2, 100.4(2) (average); (Et2N)3PSeI2, 106.4(1)] whereas the Se-I-I linkages are all essentially linear [173.69(6), 174.98(8) (average); 178.04(5)]. These results are interpreted as a donation of electron density from the selenium atom to the sigma*-antibonding orbital of the diiodine.

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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 interaction of hydrospirophosphoranes with square-planar d8 rhodium(I) complexes was studied.The structures of the complexes formed are discussed on the basis of IR, 31P, 15N and 13C NMR and X-ray electron spectral data.

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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 Cotton-Mouton and Kerr effects were used to determine the molecular magnetic and electric anisotropies of the hexamethyl triamides of phosphorous, phosphoric, and thiophsphoric acids.The anisotropies of the phosphoryl and thiophosphoryl groups were calculated.The magnetic anisotropies of these bonds depend on the immediate environment at the phosphorous atom and correlate linearly with the ?P reactivity constant.

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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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Nucleophilic addition of tris(dialkylamino) phosphines, P(NR2)3 (R = Me or Et, nPr), to [Fe2(CO)6(mu-PPh2){mu-eta 1:eta2-(H)Calpha=Cbeta=C gammaH2}] (1) affords the dimetallacyclopentene derivatives [Fe2(CO)6(mu-PPh2)(mu-eta 1:eta1-HC=C{P(NR2)3}CH 2)] (R = Me, 2a; R = Et, 2b; R = nPr, 2c) or a mixture of the vinylidene- and dimetallacyclobutene-bridged complexes [Fe2(CO)6(mu-PPh2)-(mu-eta 1-C=C(CH3){P(NMe2)3})] (3a) and [Fe2(CO)6(mu-PPh2)(mu-eta 1:eta1-(CH3)C=C{P(NMe2) 3})] (4a), respectively, depending upon the reaction conditions. For instance, addition of P(NR2)3 to an ether solution of [Fe2(CO)6(mu-PPh2){mu-eta 1:eta2-(H)Calpha=Cbeta=C gammaH2}] gave the dimetallacyclopentenes 2a-c, whereas pretreatment of a solution of the allenyl starting material with HBF4 prior to the addition of P(NR2)3 gave the vinylidene- and dimetallacyclobutene-bridged products, which co-crystallized as a 67:33 mixture, as determined by single-crystal X-ray crystallography and 1H NMR spectroscopy. We have subsequently shown that the sigma-eta-allenyl complex [Fe2(CO)6(mu-PPh2){mu-eta 1:eta2-(H)Calpha=Cbeta=C gammaH2}] undergoes a clean and quantitative acid-promoted rearrangement to the sigma-eta-acetylide-bridged isomer [Fe2(CO)6(mu-PPh2){mu-eta1: eta2-C?CH3}] (5). 1H NMR and deuterium labeling studies suggest that this isomerization occurs via initial protonation at Cgamma to afford a kinetic intermediate which rapidly rearranges to its thermodynamically more stable propyne-bridged counterpart followed by deprotonation. Clearly, the vinylidene and dimetallacyclobutene products isolated from the reaction between 1 and tris(dialkylamino) phosphine in the presence of acid arise from nucleophilic addition to the alpha- and beta-carbon atoms of the acetylide bridge in [Fe2(CO)6(mu-PPh2){mu-eta 1:eta2-C?CCH3}], and not from nucleophilic addition followed by hydrogen migration. In refluxing toluene, the dimetallacyclopentenes [Fe2(CO)6(mu-PPh2)(mu-eta 1:eta1-HC=C{P(NR2)3}CH 2)J slowly decarbonylate to give [Fe2(CO)5(mu-PPh2)(mu-eta 1:eta3-C(H)C{P(NR2)3}CH 2)] (R = Me, 6a; R = Et, 6b; R = nPr, 6c) bridged by a sigma-eta3-coordinated vinyl carbene. In the case of R = Et and nPr a competing isomerization also affords the highly unusual zwitterionic alpha-phosphoniumalkoxide-functionalized sigma-sigma-alkenyl complex [Fe2(CO)5(mu-PPh2){mu-eta 1:eta2-{P(NR2)3}C(O)CHC= CH2}] (R = Et, 7b; R = nPr, 7c), via a P(NR2)3-carbonyl-allenyl coupling sequence. In contrast, isomerization of dimetallacyclopentene [Fe2(CO)6(mu-PPh2)(mu-eta 1:eta1-HC=C{PPh3}-CH2)] (8) to its sigma-eta-alkeny] counterpart [Fe2(CO)5(mu-PPh2){mu-eta 1:eta2-PPh3C(O)CHC=CH2}] (9) is essentially complete within 1 h at room temperature with no evidence for the formation of the corresponding vinyl carbene. Thermolysis of a toluene solution of 8 in the presence of excess P(NEt2)3 results in exclusive formation of 7b, whereas at room temperature phosphine substitution affords 2b, via PPh3-P(NEt2)3 exchange. The isomerization of 8 to 9 and 2b,c to 7b,c appears to involve a dissociative equilibrium between the kinetic regioisomeric intermediate dimetallacyclopentene and 1, nucleophilic attack of phosphine at a carbonyl ligand of 1 to give a zwitterionic acylate intermediate, followed by acyl-allenyl coupling to afford the thermodynamically favored zwitterionic sigma-eta-alkenyl derivative. Qualitatively, the rate of isomerization increases as the steric bulk of the phosphine increases, in the order P(NMe2)3 < P(NEt2)3 ? P(NnPr2)3 < PPh3. The single-crystal X-ray structures of 2a, 3a, 4a, 6b, 7b, 8, and 9 are reported. Do you like my blog? If you like, you can also browse other articles about this kind. category: chiral-phosphine-ligands. Thanks for taking the time to read the blog about 1608-26-0

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