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Totally stereoselective P-O to P-C migration rearrangement: Application to the synthesis of new chiral O-hydroxyaryl phosphine oxides

The synthesis of a novel class of chiral o-hydroxyaryl phosphine oxides by the rearrangement of a P-O to a P-C bond is described. This reaction proceeds with excellent yields (75-95%) and total retention of the configuration on the phosphorus atom. In the case of the treatment of an equimolar mixture of the diastereomers anti-2e and syn-2f, the resulting compounds anti-3e and syn-3f, obtained in a 1:1 molar ratio, were separated and characterized by X-ray diffraction. On the basis of the experimental results, we suggest that the migration mechanism is addition-pseudorotation-elimination; this explains the total stereoselectivity observed at the phosphorus atom.

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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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Synthesis and multinuclear NMR study (1H, 11B, 13C, 14N, 15N, 31P, 77Se) of N-azolyl-phosphorus compounds

The synthesis of N-azolyl (pyrrole, pyrazole, 1,2,4-triazole) phosphorus compounds containing PIII or PV is described.The title compounds were studied by multinuclear NMR (1H, 11B, 13C, 14N, 15N, 31P, 77Se) with particular emphasis on <15N> NMR parameters.Experimental details are given for the natural abundance <15N>NMR spectra and advantage of the various techniques is discussed.The comparison between values 1J(31P15Nazole) and 1J(31P15Nalkyl) shows that the nature of the lone electron pair of the trigonal nitrogen atoms of the minor importance as far as the changes in the magnitude of the coupling constants are concerned.Sterical interactions and inductive effects are reflected by the <15N>NMR parameters.Both PIII and PV appear to be very weak ?-acceptors as is evident from delta15N and delta13C values.P-N(dp)? interactions are hardly reflected by <15N>NMR parameters.

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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 arylaldehydes with hexamethylphosphorous triamide and the use of the resulting products for the synthesis of enamines and deoxybenzoins

The reaction between the arylaldehydes 1a,b and hexamethylphosphorous triamide 2 leads to the [aryl(dimethylamino)methyl]phosphonic bis(dimethylamides) 3a,b. These can be easily deprotonated by butyllithium in 1,2-dimethoxyethane and condensed with arylaldehydes to afford enamines 4a-f or deoxybenzoins 5a-f in fair to 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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Transition-metal Chemical Shifts in Complexes of Molybdenum(0) and Tungsten(0)

Molybdenum-95 and tungsten-183 n.m.r. spectra have been measured by direct observation and by multiple-resonance methods respectively for 65 related derivatives of and with (mainly) phosphorus ligands.The chemical shifts of the two nuclei are remarkably parallel, those for (183)W being ca. 1.7 times more sensitive to changes in chemical environment than those for (95)Mo.The chemical shifts are temperature-dependent, and trends in them can be largely accounted for by variations in the mean electronic excitation energy.The metal-phosphorus spin-coupling constants are very predictable.Molybdenum-95 linewidths in many cases are quite small, and can be broadly explained by the use of a point-charge model.

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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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Systematic kinetics of high-nuclearity metal carbonyl clusters. Exceptional behavior of Ru5C(CO)15 with P-donor nucleophiles

The kinetics of reactions of the high-nuclearity carbonyl cluster (HNCC), Ru5C(CO)15, with 21 P-donor nucleophiles, L, to form Ru5C(CO)14 L have been studied. The nucleophiles were chosen such that their electronic (pKa? = -2.79 to 12.20) and steric (Tolman cone angles, theta= 101-182) properties are systematically varied. With 10 smaller nucleophiles (theta ? 133) the reactions occur via two well-separated steps: adduct formation and CO-dissociation from the adducts to form the monosubstituted products. The structures of the adducts formed are shown spectroscopically to be closely related to others reported and structurally characterized elsewhere. The rate equations for the two steps are effectively kobs = k+L[L] and kobs = k-cO, respectively. With 11 larger nucleophiles (theta ? 136) the reaction is a quite different, second-order one-step, process with no spectral evidence for adduct formation being observed. Quantitative analysis of the dependence of the various rate constants on the electronic and steric properties of the nucleophiles or ligands involved shows that adduct formation of this HNCC with the group of smaller nucleophiles is much more facile than any comparable nucleophile-dependent reactions of other metal carbonyls. The rates of loss of CO from the adducts are decreased both by increasing net electron donicity of the ligands involved and by increasing the size of those ligands. The rate constants for the single-step reactions with the group of larger P-donors depend on the latters’ electronic and steric properties in a way showing that major expansion of the cluster is required to form the transition states and this is only possible by virtue of an exceptionally high degree of Ru-nucleophile bond-making. The flexibility of the transition state, once formed, is exceptionally low.

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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 GENERAL SYNTHESIS OF OPTICALLY ACTIVE PHOSPHINES, PHOSPHINITES AND THIOPHOSPHINITES FROM ALKYLTHIO(ALKYLSELENO)PHOSPHONIUM SALTS AND TRIS(DIMETHYLAMINO)PHOSPHINE AS A THIOPHILIC AGENT

Tris(dimethylamino)phosphine was found to be a suitable thiophilic reagent which converts optically active alkylthio(alkylseleno)phosphonium salts into chiral tertiary phosphines and phosphonites with a high stereoselectivity.The first synthesis of optically active thiophosphinites from bis(alkylthio)phosphonium salts and tris(dimethylamino)phosphine is also reported.

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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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Effective synthesis of cyclic carbonates from carbon dioxide and epoxides by phosphonium iodides as catalysts in alcoholic solvents

Phosphonium iodides effectively catalyzed the reaction of CO2 and epoxides under mild conditions such as ordinary pressure and ambient temperature in 2-propanol, and the corresponding five-membered cyclic carbonates were obtained in high yields.

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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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Synthesis and conformational analysis of phosphorus-derivatized no-base analogues of 3′,5′-cyclic nucleotides

A number of epimeric pairs of 3-X-3-oxo-trans-2,4,7-trioxa-3-phosphabicyclo<4.3.0>-nonanes <5, X=OCH3; X=OPh; 7, X=Cl; 8, X=N(CH3)2; 9, X=S(1-); 10, X=O(1-)> have been prepared as no-base analogues of 3′,5′-cyclic nucleotides. 1H NMR analysis shows the phosphate ring of the cis diastereomers (relationship of singly bonded substituent on phosphorus and proton H1) 5a-7a, 9a and 10 and the trans diastereomers 8b and 9b to be in chair conformation 15.The phosphate rings of the epimers 5b-7b and 8a exist as an equilibrium between chair conformation 15 and twist conformation 16.The mole fraction of twist depends on the nature of singly bonded substituent and varies from about 0.3 for 5b to 0.8 for 7b.The close similarity in coupling constants of the tetrahydrofuran ring of the phosphates 5-10 indicates that the population of a twist conformer has little effect on the conformation of this ring, which is close to 4E-4T3.The results obtainaed for 5-10 are compared with those of conformational studies on corresponding phosphates derived from thymidine and cyclopentane.

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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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, molecular formula is P[N(CH3)2]3. In a Article,once mentioned of 1608-26-0, category: chiral-phosphine-ligands

Deprotonation of calixarenes in acetonitrile

The pKa values for calixarenes in MeCN have been determined by selective titration with bases using a spectroscopic method. These values are as follows: calix[4]arene pKa(1) = 19.06 ± 0.22, pK a(2) > 33; calix[6]arene pKa(1) = 15.59 ± 0.06, pKa(2) = 23.85 ± 0.35, pKa(3) > 33; calix[8]arene pKa(1) = 17.20 ± 0.20, pKa(2) = 20.32 ± 0.31, pKa(3) > 33. The trends in acidity are rationalized using structures generated by a DFT model. For mono-deprotonation, the degree and nature of hydrogen bonding in the anion is the dominant factor; for di-deprotonation, spatial separation of the anionic charges becomes important.

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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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Synthesis of transient and stable C-amino phosphorus ylides and their fragmentation into transient and stable carbenes

Only basic phosphines, such as tris(dimethylamino)phosphine, allow for the synthesis of a stable acyclic beta-amino phosphonium salt 1c, which upon deprotonation with butyllithium affords the corresponding stable C-amino phosphorus ylide 2c. In contrast, cyclic beta-amino phosphonium salts 5a and 5b are stable despite the presence of weakly basic triarylphosphine fragments. They are prepared by intramolecular insertion of the carbene center of (amino)(phosphonio)carbenes into the CH bond of a phosphorus substituent. Deprotonation of 5a leads to the corresponding cyclic C-amino phosphorus ylide 6a, which has been fully characterized including an X-ray diffraction study. Deprotonation of 5b affords enamine 8, probably via fragmentation of ylide 6b into transient carbene 7b and a subsequent 1,2-hydrogen shift. Transient cyclic C-amino phosphorus ylides 6c and 6d have been prepared by intramolecular addition of a carbanion generated by deprotonation of a phosphorus substituent. Three-membered heterocycle 6c rearranges into alkene 9, whereas the four-membered ring system undergoes a ring opening affording the stable carbene 7d. The latter results pave the route for the synthesis of various mixed carbene-phosphine bidentate ligands.

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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