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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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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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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.

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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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New modular P-chiral ligands for Rh-catalyzed asymmetric hydrogenation

New modular P-chiral ligands have been prepared from commercially available (S)-alpha,alpha-diphenylprolinol. With these new types of ligands, up to 95% ee was achieved in the Rh-catalyzed asymmetric hydrogenation of functionalized olefins.

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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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Synthesis of penta- and hexa-m-phenylenecyclophosphites and thiophosphates

New representatives of an original crown ether class-penta- and hexaresorcinolamidophosphites (7a,b and 13a,b)-were synthesized using the molecular assemblage technique. Their thio derivatives (8a,b and 14a,b) were obtained, as well as the rhodium (I) complex of hexaphosphite 13b (16). Macrocycle 15 containing both P3+ and P5+ was synthesized. 1H and 31P NMR spectroscopy data suggested the higher conformational flexibility of phosphite macrocycles.

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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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Novel Di-isopropylamino Derivatives of Trivalent Phosphorus

Reduction of (iPr2N)2PCl with LiAlH4 in diethyl ether gives (iPr2N)2PH; reaction of iPr2NPCl2 with Mg in boiling tetrahydrofuran gives either the cyclotetraphosphine (iPr2N)4P4 or the 1,2-dichlorobiphosphine iPr2NP(Cl)-P(Cl)NiPr2 depending upon the Mg:iPr2NPCl2 mole ratio.

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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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Effect of isopropyl group on phosphorylation of phenols with phosphorous amides

Reaction of resorcinol with phosphorous triamides containing various aliphatic radicals was studied. The preferential cleavage from phosphorus of the diisopropylamino group compared with the less bulky dimethylamino group was observed for the first time. It was shown that resorcinol is easily phosphorylated under mild conditions independent of the nature of substituent on nitrogen, but sterically hindered bulky radicals on nitrogen slow down phenolysis not only of the first, but also of the second amido group.

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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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Spirophosphoranes from the Reaction of Disalicylaldimines with Trivalent Phosphorus Acid Amides

A new approach to the synthesis of spirophosphoranes 9, 11, 15a-c containing P-C, P-O, and P-N intramolecular bonds was developed. It is based on the reaction of trivalent phosphorus acid amides with bis(o-hydroxyaryl)diimines. The composition and structure of the products obtained were confirmed by NMR methods, IR spectroscopy, elemental analysis and X-ray analysis.

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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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Reactions of trisdialkylaminophosphines with acrylohydrazide and imidazolinone derivatives for the synthesis of new organophosphorus derivatives

Trisdimethylaminophosphine reacts with 2-benzamido-N-arylidene-3-aryl- acrylohydrazide to give phosphoryl benzamide and phosphoryl-cyano-benzamide adducts depending on the reaction conditions. Moreover, 1-aryliden-amino-2- phenyl-4-aryliden-2-imidazolin-5-ones react with trisdialkylaminophosphines to yield tetraalkylphosphonic diamide adducts. Possible reaction mechanisms are considered, and the structural assignments are based on analytical and spectroscopic evidence and X-ray analysis. Copyright Taylor & Francis Group, LLC.

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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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Synthesis and Transformation of Glycosyl Azides

Owing to their functional group, glycosyl azides (general structure Glyc-N3) constitute important and versatile derivatives for carbohydrate chemistry. Because of the dipole character of organic azides (see resonance structures A, B, and C) they can function both as nucleophiles and electrophiles, and readily undergo dipolar cycloadditions. Further, as configurationally stable groups, azides are well suited as starting materials for formation of other nitrogen-containing functionalities, such as amines, amides, ureas, carbodiimides, and others.{A figure is presented}. The current article ties in with previous ones that were published in 19611 and 1993.2 In the past decade there have been reports on a number of relevant preparative approaches and uses of anomeric glycosyl azides, which provide a plethora of synthetic options for carbohydrate chemistry.

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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