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, 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.

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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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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.

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.

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, 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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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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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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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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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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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.

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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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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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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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Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.name: Tris(dimethylamino)phosphine
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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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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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, molecular formula is P[N(CH3)2]3. In a Article£¬once mentioned of 1608-26-0

X-ray and 1H NMR Studies of the Conformational Equilibria of 2-Z-3-Phenyl-1,3,2-oxazaphosphorinanes. Steric and Stereoelectronic Influences on the Unexpected Axial Preferences of Me2N and MeNH Substituents on Three-Coordinate Phosphorus

A series of 2-Z-3-phenyl-1,3,2-oxazaphosphorinanes 7-14 (Z = MeO, (CF3)2CHO, Ph, MeNH, and Me2N) containing three-coordinate phosphorus was prepared.The conformations of the six-membered rings were investigated by 1H and 31P NMR spectroscopy and X-ray crystallography.The rings with substituents MeO, (CF3)2CHO, Ph, and MeNH on phosphorus can be unambiguously assigned in solution to a single chair conformation with the substituent of phosphorus axial.An X-ray crystal structure of 5,5-dimethyl-2,3-diphenyl-1,3,2-oxazaphosphorinane, 11, reveals a chair form ring with the phenyl group attached axially to phosphorus.For 13 and 14 with a Me2N substituent on phosphorus, a chair-chair equilibrium (20 ->/<- 21) is found in solution that features an 80-90percent population (DeltaG0 = 0.9-1.1 kcal/mol) of the Me2N axial conformation (20).This finding contrasts sharply with the known 1 kcal/mol preference for the Me2N to be equatorial in the corresponding 2-(dimethylamino)-1,3,2-dioxaphosphorinanes.The ability of the 1,3,2-oxazaphosphorinane ring to accommodate the Me2N substituent axially is also seen in the X-ray crystal of 5,5-dimethyl-3-phenyl-2-(dimethylamino)-1,3,2-oxazaphosphorinane, 13, which features a chair conformation ring that is considerably distorted compared to that of 11, quite evidently to allow the Me2N to be in the observed axial orientation, conformation 20.It is argued that the axial orientation of the Me2N in 13 and 14 is at least partly in response to steric repulsions in the alternative chair conformation 21 between the equatorial Me2N and the phenyl substituent at N(3).This effect is in direct contrast to the repulsive interactions between the N(3)Ph and axial Me2N on phosphorus previously demonstrated for four-coordinate, 2-oxo-1,3,2-oxazaphosphorinanes.The increased bond lengths within the 1,3,2-oxazaphosphorinane ring over its 1,3,2-dioxaphosphorinane counterpart (C-N vs C-O) and increased ring flexibility, along with potential n->?* stereoelectronic factors of the type operative in the anomeric effect, are also proposed as potential contributors to the preferred axial orientation of Me2N in 13 and 14.The diastereomeric molecules cis- and trans-5-tert-butyl-3-phenyl-2-(dimethylamino)-1,3,2-oxazaphosphorinane, 17, also were prepared.At thermodynamic equilibrium at room temperature, cis-17 (2-Me2N and 5-t-Bu groups cis) is favored (cis/trans = 80/20). cis-17 displays a conformational equilibrium (Scheme 1) involving a chair conformer (ca. 60percent) with the t-Bu equatorial and Me2N axial, cis-17a, and a single twist or boat form with both substituents pseudoequatorial, cis-17d (ca. 40percent). trans-17 exists in solution in three conformations in apptoximately equal populations: a chair form with both t-Bu and Me2N equatorial (trans-17a) and two boat/twist forms (trans-17b and trans-17c) with the t-Bu pseudoequatorial and the Me2N pseudoaxial.The distributions of chair and boat/twist conformations can be reasonably understood in terms of the same 1,3-syn …

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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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, molecular formula is P[N(CH3)2]3. In a Article£¬once mentioned of 1608-26-0

Thio effects on the departure of the 3?-linked ribonucleoside from diribonucleoside 3?,3?-phosphorodithioate diesters and triribonucleoside 3?,3?,5?-phosphoromonothioate triesters: Implications for ribozyme catalysis

To provide a solid chemical basis for the mechanistic interpretations of the thio effects observed for large ribozymes, the cleavage of triribonucleoside 3?,3?,5?-phosphoromonothioate triesters and diribonucleoside 3?,3?-phosphorodithioate diesters has been studied. To elucidate the role of the neighboring hydroxy group of the departing 3?-linked nucleoside, hydrolysis of 2?,3?-O-methyleneadenosin-5?-yl bis[5?-O-methyluridin-3?-yl] phosphoromonothioate (1a) has been compared to the hydrolysis of 2?,3?-O-methyleneadenosin-5?-yl 5?-O-methyluridin-3?-yl 2?,5?-di-O-methyluridin- 3?-yl phosphoromonothioate (1b) and the hydrolysis of bis[uridin-3?- yl] phosphorodithioate (2a) to the hydrolysis of uridin-3?-yl 2?,5?-di-O-methyluridin-3?-yl phosphorodithioate (2b). The reactions have been followed by RP HPLC over a wide pH range. The phosphoromonothioate triesters 1a,b undergo two competing reactions: the starting material is cleaved to a mixture of 3?,3?- and 3?,5?-diesters, and isomerized to 2?,3?,5?- and 2?,2?,5?-triesters. With phosphorodithioate diesters 2a,b, hydroxide-ion-catalyzed cleavage of the P-O3? bond is the only reaction detected at pH > 6, but under more acidic conditions desulfurization starts to compete with the cleavage. The 3?,3?-diesters do not undergo isomerization. The hydroxide-ion-catalyzed cleavage reaction with both 1a and 2a is 27 times as fast as that compared with their 2?-O-methylated counterparts 1b and 2b. The hydroxide-ion-catalyzed isomerization of the 3?,3?,5?-triester to 2?,3?,5?- and 2?,2?,5?-triesters with 1a is 11 times as fast as that compared with 1b. These accelerations have been accounted for by stabilization of the anionic phosphorane intermediate by hydrogen bonding with the 2?-hydroxy function. Thio substitution of the nonbridging oxygens has an almost negligible influence on the cleavage of 3?,3?-diesters 2a,b, but the hydrolysis of phosphoromonothioate triesters 1a,b exhibits a sizable thio effect, kPO/kPS = 19. The effects of metal ions on the rate of the cleavage of diesters and triesters have been studied and discussed in terms of the suggested hydrogen-bond stabilization of the thiophosphorane intermediates derived from 1a and 2a.

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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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Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.name: 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.

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

Galactose-derived phosphonate analogues as potential inhibitors of phosphatidylinositol biosynthesis in mycobacteria

Galactose-based phosphonate analogues of myo-inositol-1-phosphate and phosphatidylinositol have been synthesized from methyl beta-d- galactopyranoside. Michaelis-Arbuzov reaction of isopropyl diphenyl phosphite or triisopropyl phosphite with a 6-iodo-3,4-isopropylidene galactoside afforded the corresponding phosphonates. Deprotection of the diphenyl phosphonate afforded methyl beta-d-galactoside 6-phosphonate, an analogue of myo-inositol-1-phosphate. The diisopropyl esters of the diisopropyl phosphonate were selectively deprotected and the corresponding anion was coupled with 1,2-dipalmitoyl-sn-glycerol using dicyclohexylcarbodiimide. Deprotection afforded a methyl beta-d-galactoside-derived analogue of phosphatidylinositol. The galactose-derived analogues of phosphatidylinositol and myo-inositol-1-phosphate were not substrates for mycobacterial mannosyltransferases (at concentrations up to 1 mM) involved in phosphatidylinositol mannoside biosynthesis in a cell-free extract of Mycobacterium smegmatis. The galactose-derived phosphonate analogue of phosphatidylinositol was shown to be an inhibitor at 0.01 mM of PimA mannosyltransferase involved in the synthesis of phosphatidylinositol mannoside from phosphatidylinositol, and a weaker inhibitor of the next mannosyltransferase(s), which catalyzes the mannosylation of phosphatidylinositol mannoside. This journal is The Royal Society of Chemistry.

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.name: 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