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[Figure not available: see fulltext.] This review provides a generalized and systematized analysis of literature data from the last 15 years regarding the methods of synthesis and properties of bi- and tricyclic assemblies constructed from 1,3-thiazolidine/thiazoline rings that are linked by an exocyclic ?=? double bond. Examples of such assemblies which are of interest as biologically active compounds, sensitizing dyes for solar cells, and semiconductors are considered in details. The literature data have been arranged according to the types of chemical 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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KHFe(CO)4 reacts with tris(amino)phosphines by substitution at phosphorus leading to [bis(amino)phosphine]tetracarbonyliron complexes [(R1R2N)2PH]Fe(CO)4. The X-ray structure has been determined for R1=R2=Ph. Deprotonation of these complexes with KH affords stable potassium phosphidotetracarbonylferrates which can be alkylated or acylated at phosphorus.

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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 cis effects of phosphine, arsine and stibine ligands have been evaluated by measuring the IR stretching frequency in dichloromethane of the carbonyl ligand in a series of Rh(I) Vaska-type complexes, trans-[RhCl(CO)(L) 2]. These data were correlated with those obtained by Tolman for the electronic trans influences in the [Ni(L)(CO)3] complexes. The electronic contribution, chiFc, of ferrocenyl was determined as 0. 8 from these plots by evaluating PPh2Fc as ligand. In order to accommodate arsine and stibine ligands an additional correction term, to compensate for differences in the donor atom, was added to Tolman’s equation for calculation of the Tolman electronic parameter of phosphine ligands. In the resulting equation: nu(CONi)=2056.1+?i=1 3chii+CL values for CL of C P=0, CAs=-1.5 and CSb=-3.1 are suggested for phosphine, arsine and stibine ligands, respectively. The crystal and molecular structures of trans-[RhCl(CO)(PPh2Fc)2]¡¤2C 6H6, trans-[RhCl(CO){P(NMe2)3} 2] and trans-[RhCl(CO)(AsPh3)2] are reported. The Tolman cone angles for PPh2Fc and P(NMe2)3 were determined as 169 and 166, while the effective cone angles for PPh2Fc, P(NMe2)3 and AsPh3 were determined as 171, 168 and 147, respectively.

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Reference£º
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 FOR ASYMMETRIC SYNTHESIS, LIGAND FOR USE THEREIN, AND PROCESS FOR PRODUCING OPTICALLY ACTIVE COMPOUND THROUGH ASYMMETRIC SYNTHESIS REACTION USING THEM

Compounds represented by the following general formula (1a) or (1b). A complex comprising a center metal of rhodium and a compound represented by the following general formula (1a) or (1b) as a ligand. A catalyst for optically active beta-substituted carbonyl compound synthesis and catalyst for asymmetric 1, 2 addition reaction being composed of the complex. A method of production of an optically active beta-aryl compound from an alpha, beta-unsaturated compound and an aryl-boronic acid derivative and method of production of an optically active aryl alcohol compound from an aldehyde compound and aryl boronic acid derivatives using the catalyst. A complex comprising a center metal of palladium and a compound represented by the following general formula (1a) or (1b) as a ligand. A catalyst for asymmetric allylic substitution reaction being composed of the complex. A method of production of an optically active dialkyl (1,3-disubstituted propeny)malonate compound from a 1,3- disubstituted ally acetate compound and a dialkyl malonate and method of production of an optically active allylamine compound from a 1,3-disubstituted ally acetate compound and an amine compound. The compounds have not only the versatility of being usable in the synthesis of wide-ranging optically active aryl compounds but also the selectivity and reactivity permitting synthesis with high yield within a short period of time under industrially advantageous mild conditions.

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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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Formation of the fullerene radical anion in the reaction of C60 with phosphorous triamides

Fullerene C60 reacts with phosphorous acid triamides to give the radical anion.

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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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SYNTHESE UND REAKTIVITAET VON DIENYLMETALL-VERBINDUNGEN. XVI. CYCLOPENTADIENYLNICKEL-KOMPLEXE MIT HEXAALKYL-PHOSPHORIGSAEURETRIAMID-LIGANDEN

Complexes of the type C5H5Ni(P(NR2)3)X (X = Cl, Br, CH3) and PF6 (R = CH3, C2H5) are prepared.CH3OH cleaves the phosphorus-nitrogen bond.

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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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Chemistry of Phosphorus Ylides: Part 46?Efficient Synthesis and Biological Evaluation of New Phosphorus, Sulfur, and Selenium Pyrazole Derivatives

1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carbaldehyde was allowed to react with different phosphorus, sulfur, and selenium reagents. The reaction products depend on the nature of the reagent and the condition of the reaction used. Treatment of the carbaldehyde with the active phosphacumulene ylides afforded the phosphoranylidene pyranopyrazoles. On the other hand, its reaction with the stable phosphonium ylides gave the oxaphosphetanes. Sulfidodithiaphosphetane pyrazole was generated from the reaction of Japanese reagent with the carbaldehyde. Selenido-oxaselenaphosphetane and dioxaphospholane pyrazoles were obtained from the reaction of the carbaldehyde with Woolin’s reagent and phosphorus triamide, respectively. The antimicrobial screening of the synthesized compounds was also evaluated.

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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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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