Category: 1608-26-0

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YLURES SANS SEL, EVOLUTION EN PHOSPHORANES ET EQUILIBRE YLURE <*> PHOSPHORANE I. SYNTHESE ET STRUCTURE

Synthesis of new salt-free ylids 9, 12 to 16, 19, 20, 22, 27 and 29 and phosphoranes 10, 17, 18, 21, 23, 30 to 33 by addition of a trivalent phosphorus compound (phosphites and amino-phosphines) 1 to 7 with dimethyl acetylenedicarboxylate in presence of a protic trapping reagent are described.The results are consistent with trapping of carbanionic species.In relation with the cyclic or acyclic structure of the trivalent phosphorus compound and the protic trapping reagent ie: methanol, phenol, carboxylic acid, etc.., several pathways are involved.Clearly, three phenomena are shown: one can obtain an ylid via a phosphorane or conversely a phosphorane via an ylid or an equilibrium phosphorane <*> ylid.Results are dealing with thermodynamic or kinetically controlled reactions.

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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

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 1608-26-0, Name is Tris(dimethylamino)phosphine
, molecular formula is P[N(CH3)2]3. In a Article£¬once mentioned of 1608-26-0, Formula: P[N(CH3)2]3

Tetrakis(dialkylamino)cyclotetraphosphines and Bis(dialkylamino)dihalobiphosphines

Dehalogenation of R2NPCl2 (R = isopropyl or cyclohexyl) with magnesium in tetrahydrofuran gives the corresponding cyclotetraphosphines (R2N)4P4; the corresponding biphosphines (i-Pr2N)2P2X2 (X = Cl and Br) can be isolated from reactions of i-Pr2NPX2 with more limited quantities of magnesium.Dehalogenations with magnesium of R2NPCl2 derivatives having R2N groups smaller than diisopropylamino lead to redistribution of the dialkylamino groups giving (R2N)2P-P(NR2)2 (R2N = piperidino) or (R2N)3P (R2N = diethylamino or dimethylamino).Such redistribution reactions can be suppressed but not eliminated by using the homogenous dehalogenating agent (Me3Si)2Hg in hydrocarbon solvents.The steric bulk of the diisopropylamino groups in (i-Pr2N)4P4 reduces its chemical reactivity relative to other cyclotetraphosphines; thus (i-Pr2N)4P4 is unreactive toward oxygen, carbon disulfide, potassium metal, and various metal carbonyls under conditions where other cyclotetraphosphines react with these reagents.However, the P4 ring in (i-Pr2N)4P4 is cleaved under mild conditions by hydrogen chloride as well as by bromine and iodine.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Formula: P[N(CH3)2]3. In my other articles, you can also check out more blogs about 1608-26-0

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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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. In a document type is Article, introducing its new discovery.

Transfer-dehydrogenation of alkanes catalyzed by rhodium(I) phosphine complexes

Complexes of the form Rh(PMe3)2ClL’ (L’ = CO or trisubstituted phosphine) and [Rh(PMe3)2Cl]2 have previously been reported to catalyze the transfer-dehydrogenation of alkanes, using olefinic hydrogen acceptors under a dihydrogen atmosphere. Such complexes are herein reported to effect transfer-dehydrogenation in the absence of H2 but with much lower rates and total catalytic turnovers, even at much greater temperatures. Analogs with halides other than chloride (Br, I), or with pseudo-halides (OCN, N3), are found to exhibit generally similar behavior: high catalytic activity under H2 and measurable but much lower activity in the absence of H2. Thermolysis (under argon) of complexes [RhL2Cl]n (n = 1, 2; L is a phosphine bulkier than PMe3) in cyclooctane in the absence of hydrogen acceptors yielded cyclooctene. However, transfer-dehydrogenation was plagued by ligand decomposition. Under a hydrogen atmosphere complexes containing ligands much bulkier than PMe3 do not effect dehydrogenation. Complexes with tridentate ligands, eta3-PXP)RhL’ (PXP = (Me2PCH2Me2Si)2N, Me2PCH2(2,6-C6H3)CH2PMe2; L’ = CO, C2H4), were also found to catalyze thermal or photochemical dehydrogenation of cyclooctane with limited reactivity. The structure of [Rh(PMe3)2Cl]2 was determined by single-crystal diffraction. The Rh(mu-Cl)2Rh bridge of 1 is folded like that of [Rh(CO)2Cl]2, unlike that of the planar PPh3 and PiPr3 analogs.

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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

Related Products of 1608-26-0, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 1608-26-0, Name is Tris(dimethylamino)phosphine
, molecular formula is P[N(CH3)2]3. In a Article£¬once mentioned of 1608-26-0

EFFICIENT OLEFINATION WITH alpha-ALKYL CYCLIC PHOSPHONAMIDES

A variety of acyclic and cyclic aldehydes and ketones can be converted into the corresponding alkylidene, benzylidene and methoxycarbonyl alkylidene derivatives by treatment with 1,3,2-diazaphospholidine-2-alkyl-1,3-dimethyl 2-oxides (alpha-alkyl cyclic phosphonamides) under mild conditions.This olefination method is particularly useful in the case of enolizable carbonyl compounds.

The proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 1608-26-0 is helpful to your research., Related Products of 1608-26-0

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

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 1608-26-0, Name is Tris(dimethylamino)phosphine
, molecular formula is P[N(CH3)2]3. In a Article£¬once mentioned of 1608-26-0, Quality Control of: Tris(dimethylamino)phosphine

Some features of an SmI2-(Me2N)3P-THF system. Transformation of esters into dimethylamides

Sm11-intermediates generated upon addition of (Me2N)3P to a solution of SmI2 in THF exhibit the properties of a single-electron reducing agent and an N-nucleophile. In particular, N,N-dimethylamides are formed from esters.

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.Quality Control of: Tris(dimethylamino)phosphine
, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 1608-26-0, in my other articles.

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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The asymmetric synthesis of alpha-substituted alpha-methyl and alpha-phenyl phosphonic acids: Design, carbanion geometry, reactivity and preparative aspects of chiral alkyl bicyclic phosphonamides

The design, preparation, structural and spectroscopic analyses of topologically unique and enantiomerically pure alkyl phosphonamides are described. In the case of alpha-ethyl and alpha-benzyl phosphonamides, the geometry of both the secondary and tertiary carbanions was determined to be planar through deprotonation/deuteration/alkylation experiments. Stereoselective alkylations of such systems proceeded in good yields and with high diastereoselectivities. The resulting alpha,alpha-alkylated phosphonamides were hydrolyzed to give the corresponding alpha,alpha-alkyl phosphonic acids with high degrees of enantiomeric purity.

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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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Iridium-catalysed allylic substitution: Stereochemical aspects and isolation of IrIII complexes related to the catalytic cycle

Ir-catalysed allylic alkylations of enantiomerically enriched monosubstituted allylic acetates proceed with up to 87% retention of configuration using P(OPh)3 as ligand. High retention enantioselectivity of up to 86% ee in asymmetric allylic alkylations of achiral or racemic substrates is achieved with monodentate phosphorus amidites as ligands. Lithium N-tosylbenzylamide was identified as a suitable nucleophile for allylic aminations. Of particular importance is the use of lithium chloride as an additive, generally leading to increased enantioselectivities. Two (pi-allyl)IrIII complexes were characterised by X-ray crystal structure analysis and spectroscopic data.

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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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Chemoselective phosphine-catalyzed cyanoacylation of alpha-dicarbonyl compounds: a general method for the synthesis of cyanohydrin esters with one quaternary stereocenter

A chemoselective phosphine-catalyzed cyanoacylation of alpha-dicarbonyl compounds is reported. Under the catalysis of P(NMe2)3, the cyanoacylation of alpha-dicarbonyl compounds such as isatins, alpha-keto esters, and alpha-diketones with acyl cyanides exclusively proceeds under very mild conditions, affording a wide range of cyanohydrin esters bearing one quaternary stereocenter in moderate to excellent yields. It represents the first phosphine-catalyzed cyanoacylation of alpha-dicarbonyl compounds and also provides a general method to prepare fully substituted cyanohydrin esters.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Computed Properties of P[N(CH3)2]3. In my other articles, you can also check out more blogs about 1608-26-0

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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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OXYDES ET SULFURES DE BIS (OU TRIS)(AMIDINO)PHOSPHINES: SYNTHESE ET CYCLISATION EN 2-OXO (OU THIO)2,5-DIHYDRO-1,3,5,2lambda5-TRIAZAPHOSPHININES

The title compounds R13-nP(X)(N=C(R2)NH2)n (n=2,3; X=O,S) are obtained by the reaction of unsubstituted amidines R2-C(=NH)-NH2 with oxo (or thio)trichloro or organyldichlorophosphines.Isolated compounds 1 (R2=Ph) lead, with heating, to the 2-oxo (or thio) 2,5-dihydro-1,3,5,2lambda5-phosphinines 2.Compounds 1, with R2=alkyl are unstable, and lead directly to 2.P(NMe2)3 reacts with amidines in a molar ratio of 1:2 to give the 2,5-dihydro-1,3,5,2lambda3-triazaphosphinines 4; from these latter derivatives we tried unsuccessfully to prepare the corresponding dicoordinated phosphorus derivatives 7. Key words: Oxo (or thio) bis (or tris)(amidino)phosphines; 2,5-dihydro-1,3,5,2lambda5(or lambda3)-triazaphosphinines.

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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

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 1608-26-0, Name is Tris(dimethylamino)phosphine
, molecular formula is P[N(CH3)2]3. In a Article£¬once mentioned of 1608-26-0, name: Tris(dimethylamino)phosphine

Reduction-Oxidation Properties of Organotransition-metal Complexes. Part 12. Formation of Carbon-Carbon Bonds via the Oxidative Dimerisation of and the Reduction of 2+; X-Ray Crystal Structures of 2(eta5:eta’5-…

The complexes <1: cot=cyclo-octatetraene; n=0-3, L=P(NM2)3, PPh3, P(OCH2)3CMe, or P(OPh)3> undergo chemically irreversible one-electron oxidation in Ch2Cl2 at a platinum electrode.Chemical generation of the highly reactive radical cation , by oxidation of (1) with silver(I) salts or , is followed by isomerisation and dimerisation, via C-C bond formation, to give 2+ <3; n=0 or 2, L=P(OPh)3>.The crystal structure of <3; n=2, L=P(OPh)3>, as the – salt, reveals the presence of a dimeric C16H16 unit comprising two fused ring systems bonded to one another across a two-fold crystallographic axis of symmetry.The five unbridged carbon atoms of the C7 ring are coplanar and eta5-bonded to the iron atom, which in turn is orthogonally co-ordinated to the two CO ligands and the P(OPh)3 group.The C7 ring folds away from the metal atom, and there are further folds at the junction with the C3 ring and again at the apex of the C3 ring, all in the same sense.The dimeric ligand thus has an overall S shape when viewed down the two fold axis.Along the Fe<*>Fe vector, by contrast, the C3 rings are seen edgewise and the two C7 ring are almost eclipsed.Complex (3; n=0) reacts with NaBH4 to give (4).With halide ion, however, (3; n=0) affords (5) via reductive C-C coupling.X-Ray analysis shows that in complex (5) s further link between the two halves of the dimer has been formed, in that the fifth C atom of C7 rin which in (3) was bonded to the metal atom is now bonded to its counterpart in the other half of the dimer, forming an additional central C6 ring.As might be expected, the C7 ring which is not co-ordinated to iron is more nearly planar and the C-C bonds are more localised.With , complex (5) yields (6), but with NMe3O*2H2O in refluxing benzene, ring detachment results in the isolation of the free polycyclic hydrocarbon, C16H16 (7).

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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