- Generation of Axially Chiral Fluoroallenes through a Copper-Catalyzed Enantioselective β-Fluoride Elimination
-
Herein we report the copper-catalyzed silylation of propargylic difluorides to generate axially chiral, tetrasubstituted monofluoroallenes in both good yields (27 examples >80%) and enantioselectivities (82-98% ee). Compared to previously reported synthetic routes to axially chiral allenes (ACAs) from prochiral substrates, a mechanistically distinct reaction has been developed: the enantiodiscrimination between enantiotopic fluorides to set an axial stereocenter. DFT calculations and vibrational circular dichroism (VCD) suggest that β-fluoride elimination from an alkenyl copper intermediate likely proceeds through a syn-β-fluoride elimination pathway rather than an anti-elimination pathway. The effects of the C1-symmetric Josiphos-derived ligand on reactivity and enantioselectivity were investigated. Not only does this report showcase that alkenyl copper species (like their alkyl counterparts) can undergo β-fluoride elimination, but this elimination can be achieved in an enantioselective fashion.
- O'Connor, Thomas J.,Mai, Binh Khanh,Nafie, Jordan,Liu, Peng,Toste, F. Dean
-
supporting information
p. 13759 - 13768
(2021/09/07)
-
- Systematic Study of the Stereoelectronic Properties of Trifluoromethylated Triarylphosphines and the Correlation of their Behaviour as Ligands in the Rh-Catalysed Hydroformylation
-
The stereoelectronic properties of a series of trifluoromethylated aromatic phosphines have been studied using different approaches. The σ-donating capability has been evaluated by nuclear magnetic resonance (NMR) spectroscopy of the selenide derivatives and the protonated form of the different trifluoromethylated phosphines. The coupling constants between phosphorous and selenium (1JSeP) and phosphorous and hydrogen (1JHP) can be predicted by empirical equations and correlate the basicity of the phosphines with the number and relative position of trifluoromethyl groups. In contrast, the π-acceptor character of the ligands has been evaluated by measuring the frequency of the CO vibration in the infrared (IR) spectra of the corresponding Vaska type iridium complexes ([IrCl(CO)(PAr3)2], PAr3=triarylphosphine). Moreover, the correlation between the electronic properties and the performance of these phosphines as ligands in the rhodium-catalysed hydroformylation of 1-octene has been established. Phosphines with the lowest basicity, that are those with the highest number of trifluoromethyl groups, gave rise to more active catalytic systems.
- Herrera, Daniel,Peral, Daniel,Cordón, Mercedes,Bayón, J. Carles
-
supporting information
p. 354 - 363
(2020/12/30)
-
- Regiocontrolled Reductive Vinylation of Aliphatic 1,3-Dienes with Vinyl Triflates by Nickel Catalysis
-
The regiocontrolled functionalization of 1,3-dienes has become a powerful tool for divergent synthesis, yet it remains a long-standing challenge for aliphatic substrates. Herein, we report a reductive approach for a branch-selective 1,2-hydrovinylation of aliphatic 1,3-dienes with R-X electrophiles, which represents a new selectivity pattern for diene functionalization. Simple butadiene, aromatic 1,3-dienes, and highly conjugated polyene were also tolerated. The combination of Ni(0) and the phosphine-nitrile ligand generally resulted in >20:1 regioselectivity with the retention of the geometry of the C3-C4 double bonds. This reaction proceeds with a broad substrate scope, and it allows for the conjugation of two biologically active units to form more complex polyene molecules, such as tetraene and pentaene as well as heptaene.
- Pang, Xiaobo,Zhao, Zhen-Zhen,Wei, Xiao-Xue,Qi, Liangliang,Xu, Guang-Li,Duan, Jicheng,Liu, Xue-Yuan,Shu, Xing-Zhong
-
supporting information
p. 4536 - 4542
(2021/04/07)
-
- Stereochemical Alignment in Triphospha[3]ferrocenophanes
-
A series of triphospha[3]ferrocenophanes of the type Fe(C5H4-PtBu)2PX with X=H, F, Cl, Br, I, NEt2, tBu has been prepared and characterized by heteronuclear NMR spectroscopy and X-ray crystallography. Despite having three stereogenic centers, the selective formation of a reduced number of diastereomers (either one or two) has been observed for these ferrocenophanes. Theoretical calculations revealed that the inversion of the central stereogenic center inverts the frontier orbital sequence leading to either an iron or a phosphorus centered HOMO depending on the respective diastereomer. CV measurements supported these results. For the all-tert-butyl substituted [3]ferrocenophane Fe(C5H4)2(PtBu)3 a chiral staggered conformation has been found in the solid state which differs substantially from the only other all-organo substituted [3]ferrocenophane, Fe(C5H4)2(PPh)3.
- Borucki, Stefan,Kelemen, Zsolt,Maurer, Martin,Bruhn, Clemens,Nyulászi, László,Pietschnig, Rudolf
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p. 10438 - 10450
(2017/08/07)
-
- Synthesis of a Tethered myo -Inositol (1,3,4,5,6)Pentakisphosphate (IP5) Derivative as a Probe for Biological Studies
-
There is sufficient evidence to suggest that myo-inositol pentakisphosphate is a vital intermediate species in higher inositol phosphate metabolism, however, its biological roles and physiological function in cells remain uncertain. A tethered myo-inosito
- Gregory, Mark,Catimel, Bruno,Yin, Meng-Xin,Condron, Melanie,Burgess, Antony W.,Holmes, Andrew B.
-
supporting information
p. 121 - 125
(2015/12/26)
-
- Bis-2-thienyldiethylaminophosphane as a ligand in late transition metal complexes and its transformation to bis-2-thienylphosphane
-
Bis-2-thienyldiethylaminophosphane (C4H3S)2PNEt2 (1) is introduced as a ligand for late transition metal complexes ([(H3C4S)2PNEt2]nMXmLp/s
- Granitzka, Markus,Stollberg, Peter,Stalke, Dietmar
-
p. 1429 - 1440
(2015/06/16)
-
- BULK ETHYLENE OLIGOMERIZATION USING A LOW CONCENTRATION OF CHROMIUM CATALYST AND THREE-PART ACTIVATOR
-
This invention enables the "bulk" oligomerization of ethylene (i.e. the oligomerization of ethylene in the presence of the oligomer product) using a catalyst system comprising 1) a very low concentration of a chromium catalyst and 2) a three part activato
- -
-
Page/Page column 19
(2013/03/26)
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- ETHYLENE OLIGOMERIZATION PROCESS WITH ALIIMINOXANE/ORGANOBORON AS ACTIVATORS USING A HALOGENATED AROMATIC SOLVENT
-
This invention provides a two stage process for the oligomerization of ethylene in the presence of a chromium catalyst having a bridging diphosphine ligand. The process mitigates problems which may be experienced during the unsteady state conditions that
- -
-
Page/Page column 20; 21
(2013/05/23)
-
- Revisiting the phospha-Wittig-Horner reaction
-
P,P-Dichlorophosphines 2a-c (RPCl2, R = Ph (a), t-Bu (b), 2,4,6-Me3Ph (c)) and P,P-dibromophosphines 4d,e (RPBr2, R = (i-Pr)3SiC≡C (d) and H2C=CH (e)) react with triethylphosphite under Michaelis-Arbuzov conditions to give phosphinodiphosphonates 3a-e in quantitative yields. After complexation to W(CO)5 and treatment with CH3ONa, phospha-Wittig-Horner reagents 9a,b are obtained on a multigram scale in good overall yield. Phospha-Wittig-Horner reagents with unsaturated substituents at IIIP (10d,e) can be prepared in analogous procedures; however, they prevail in an unusual ylide form that allows conjugation between the lone pair and the acetylene and vinyl π-systems, respectively. Phosphinophosphonate 9a has been characterized by X-ray crystallography and is shown to react smoothly with acetone within minutes. The resulting W(CO)5-coordinated phosphaalkene is shown to dimerize to a 1,2-diphosphitane or to undergo a 1,3-proton shift depending on the reaction conditions. In addition, a one-pot synthetic sequence starting from W(CO)5-coordinated phosphinodiphosphonates 5d,e has been developed to engage compounds with vinyl and acetylene substituents in phospha-Wittig-Horner reactions.
- Arkhypchuk, Anna I.,Santoni, Marie-Pierre,Ott, Sascha
-
experimental part
p. 1118 - 1126
(2012/04/10)
-
- HEAT MANAGEMENT IN ETHYLENE OLIGOMERIZATION
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The oligomerization of ethylene using a chromium catalyst having a heteroatomic ligand is used to provide oligomerization products that are selective towards hexene and/or octene. However, such processes also typically produce some polymer as an undesired
- -
-
Page/Page column 28-29
(2012/06/16)
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- New water-soluble polyanionic dendrimers - Phosphoric and 1,3,5-benzenetricarboxylic acid derivatives
-
Simple, very efficient, and having some aspects of generality, synthesis of water-soluble, polyanionic dendrimeric polyesters with different size, polarity, and flexibility is described. These macromolecular compounds consisting of phosphate or thiophosph
- Salamonczyk, Grzegorz M.
-
supporting information
p. 10209 - 10217,9
(2020/09/02)
-
- OLIGOMENZATION OF ALPHA OLEFINS
-
The oligomerization of ethylene using a chromium catalyst having a phosphorus-nitrogen-phosphorus ("P-N-P") ligand is typically activated with an aluminoxane. The addition of an alkyl zinc, particularly diethyl zinc, has been fund to improve the productiv
- -
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Page/Page column 19
(2011/12/02)
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- P-stereogenic pinene-derived phosphoramidites and their use in copper-catalyzed conjugate additions
-
New P-stereogenic phosphoramidites based on a (-)-pinane framework were synthesized and investigated by NMR spectroscopic methods and single-crystal X-ray structural analysis. The reaction between cis-pinandiol 2 and N,N-dialkylphosphoramidous dichlorides
- Hobuss, Dennis,Baro, Angelika,Axenov, Kirill V.,Laschat, Sabine,Frey, Wolfgang
-
scheme or table
p. 384 - 392
(2011/05/07)
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- Investigations of the tautomeric equilibria between phosphane oxides and their corresponding phosphinous acids bearing electron-withdrawing perfluoroaryl groups
-
The unusual form of a phosphinous acid can be stabilized by strongly electron-withdrawing substituents such as trifluoromethyl and pentafluoroethyl groups. The less electron-withdrawing pentafluorophenyl group favors the phosphane oxide tautomer (Rf)2P(O)H in the solid state, whereas in solution a solvent-dependent equilibrium with the phosphinous acid tautomer (Rf)2POH is observed. The increasing donating ability of the solvent leads to an increasing amount of the corresponding phosphinous acid tautomer. In accord with quantum chemical calculations, the electron-withdrawing effects of the p-tetrafluoropyridyl and 2,4-bis(trifluoromethyl)phenyl groups exceed the pentafluorophenyl group and should therefore be ideally suited to stabilize the corresponding phosphinous acid tautomer (Rf)2POH. The syntheses of bis(tetrafluoropyridyl)- and bis[2,4-bis(trifluoromethyl)phenyl]phosphane oxide enabled the investigation of the solvent-dependent tautomerism by NMR spectroscopy. Introduction of the tetrafluoropyridyl group shifts the tautomeric equilibrium significantly towards the phosphinous acid. Surprisingly, the comparably electron-withdrawing but more bulky 2,4-bis(trifluoromethyl)phenyl group favors the oxide tautomer. The experimental results have been confirmed by DFT calculations. In summary, electron-withdrawing substituents stabilize the phosphinous acid tautomer, whereas it is destabilized by space-demanding groups by an increased C-P-C angle. The solvent-dependent tautomeric equilibria between secondary phosphane oxides and their corresponding phosphinous acids bearing electron-withdrawing fluoroaryl groups is reported. Copyright
- Kurscheid, Boris,Wiebe, Waldemar,Neumann, Beate,Stammler, Hans-Georg,Hoge, Berthold
-
experimental part
p. 5523 - 5529
(2012/03/09)
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- ETHYLENE TRIMERIZATION CATALYSTS COMPRISING P-N-P LIGANDS AND THEIR USE
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A new P-N-P ligand having the general formula (Ph1)(Ph2)P-N-P(Ph3)(Ph4) R2 wherein each Of Ph1, Ph2, Ph3 and Ph4 is a phenyl group bonded to a phosphorus gr
- -
-
Page/Page column 18-19
(2010/04/27)
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- Ligand effects in chromium diphosphine catalysed olefin co-trimerisation and diene trimerisation
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A series of symmetric and unsymmetric N,N-bis(diarylphosphino)amine ('PNP') ligands (Ar2PN(R)PNAr′2: R = Me, Ar2 = o-anisyl, Ar′2 = Ph, 1, R = Me, Ar2 = o-tolyl, Ar′2 = Ph, 2, R = Me, Ar2 = Ph(o-ethyl), Ar′2 = Ph, 3, R = Me, Ar2 = Ar′2 = o-anisyl, 4, R = iPr, Ar2 = Ar′2 = Ph, 5) and symmetric N,N′-bis(diarylphosphino)dimethylhydrazine ('PNNP') ligands (Ar2PN(Me)N(Me)PAr2: Ar2 = o-tolyl, 6, Ar 2 = o-anisyl, 7) have been synthesised. Catalytic screening for ethene/styrene co-trimerisation and isoprene trimerisation was performed via the in situ complexation to [CrCl3(THF)3] followed by activation with methylaluminoxane (MAO). PNNP catalytic systems showed a significant increase in activity and selectivity over previously reported PNP systems in isoprene trimerisation. Comparing the symmetric and unsymmetric variants in ethene and styrene co-trimerisation resulted in a switch in selectivity, an unsymmetric catalytic (o-anisyl)2PN(Me)PPh 2 (1) ligand system affording unique incorporation of two styrenic monomers into the co-trimer product distribution differing from the familiar two ethene and one styrene ω-substituted alkenes. Complexes of the type [(diphosphine)Cr(CO)4] 8-11 were also synthesised, the single-crystal X-ray diffraction of which are reported. We propose the mechanisms of these catalytic transformations and an insight into the effect of the ligand series on the chromacyclic catalytic intermediates. The Royal Society of Chemistry.
- Bowen, Lucy E.,Charernsuk, Manutsavin,Hey, Thomas W.,McMullin, Claire L.,Orpen, A. Guy,Wass, Duncan F.
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experimental part
p. 560 - 567
(2010/04/03)
-
- Selective synthesis of chlorophosphoramidites using ionic liquids
-
A range of chlorophosphoramidites have been prepared in ionic liquids and compared with material synthesised in molecular solvents. Through the use of ionic liquids as reaction media the moisture sensitivity and impurity issues hampering existing traditio
- Amigues, Eric J.,Hardacre, Christopher,Keane, Gillian,Migaud, Marie E.,Norman, Sarah E.,Pitner, William R.
-
scheme or table
p. 1391 - 1396
(2010/05/18)
-
- AMINO PHOSPHINE
-
A new P-N-P ligand having the formula (ortho-F-C6H4)2P-N-C(CH3)2 in which each phosphorus atom is bonded to two ortho-fluorine- substituted phenyl groups. In combination with i) a source of chromium a
- -
-
Page/Page column 22
(2008/12/04)
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- IONIC LIQUID CONTAINING PHOSPHONIUM CATION HAVING P-N BOND AND METHOD FOR PRODUCING SAME
-
An ionic liquid which contains an organic matter represented by the following general formula (1) as a cation component. The ionic liquid is stably in a liquid state over a wide temperature range and is excellent in electrochemical stability. The ionic liquid is advantageously used for applications such as electric power storage devices, lithium secondary batteries, electrical double layer capacitors, dye-sensitized solar cells, fuel cells, and reaction solvents.
- -
-
Page/Page column 20; 21
(2008/12/07)
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- Probing the importance of the hemilabile site of bis(phosphine) monoxide ligands in the copper-catalyzed addition of diethylzinc to N-phosphinoylimines: Discovery of new effective chiral ligands
-
(Chemical Equation Presented) The hemilabile ligand Me-DuPHOS(O) 2 has proven to be a successful ligand for the copper-catalyzed addition of diethylzinc to N-phosphinoylimines. The corresponding α-chiral amines were obtained in high yields (80-98%) and enantiomeric ratios (19.0:1 to 99.0:1 er). Furthermore, this Cu?2 catalytic system has been shown to be effective in the addition of diethylzinc to nitroalkenes and in the reduction of β,β-disubstituted vinyl phenyl sulfones. This paper describes a general structure/selectivity study in which the three ligand subunits (chiral phospholane-linker-labile coordinating group (Z)) are systematically modified and tested in the copper-catalyzed addition of diethylzinc to the N-phosphinoylimine 1 derived from benzaldehyde. This study led to the discovery of a new class of effective chiral ligands that combine a chiral phospholane unit and an achiral phosphine oxide.
- Bonnaventure, Isabelle,Charette, Andre B.
-
p. 6330 - 6340
(2008/12/22)
-
- Preparation of biphosphine ligands for incorporation into catalytic complexes
-
This invention relates to processes for making phosphorus compounds R2P—X—PR2, R2P—M, R2P—L and R3P, and the novel cation R2P+(L)—X—P+(L)R2, where R represents an optionally substituted hydrocarbyl group, X represents a bridging group, L represents a leaving group and M represents an alkali metal atom. The invention relates further to a process for making a compound R2P—L from a compound R—H via a new process for making the compound R—Li followed by its reaction with a compound Hal2P—L. The compound R2P—X—PR2is a ligand suitable for making catalysts for copolymerizing carbon monoxide and a olefinically unsaturated compound.
- -
-
-
- The first example of palladium catalysed non-perfectly alternating copolymerisation of ethene and carbon monoxide
-
Non-alternating ethene-CO copolymerisation is catalysed by a new series of [P-O]Pd catalysts based on ?-alkoxy derivatives of diphenylphosphinobenzene sulfonic acid.
- Drent, Eite,Van Dijk, Rudmer,Van Ginkel, Roel,Van Oort, Bart,Pugh, Robert I.
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p. 964 - 965
(2007/10/03)
-
- 5,16-Dialkyl(diaryl)-5,16-dihydro-5,16-diphospha-tetraepoxy[22]annulene (2.1.2.1)
-
Several 5,16-dialkyl(diaryl)-5,16-dihydro-5,16-diphospha-tetraepoxy[22]annulenes (2.1.2.1) 9 as possible precursors of aromatic 5,16-diphospha-tetraepoxy[22]annulenes(2.1.2.1) 8 are synthesized by cyclizing Wittig-reactions of the phosphane dialdehydes 15 with the bis-ylids of the phosphane-bisphosphoniumsalts 19.
- M?rkl, Gottfried,Amrhein, Jürgen,Stoiber, Thomas,Striebl, Ulrich,Kreitmeier, Peter
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p. 2551 - 2567
(2007/10/03)
-
- Photo-Arbuzov rearrangements of cyclic phosphite systems
-
The direct UV irradiation of cyclic phosphites 1-4 was carried out in argon-saturated solvents. In all cases examined, the rearranged, ring-contracted Photo-Arbuzov phosphonate was the major product formed with isolated yields ranging from 40 to 50%. Thes
- Landis, Margaret S,Turro, Nicholas J,Bhanthumnavin, Worawan,Bentrude, Wesley G
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p. 239 - 246
(2007/10/03)
-
- The study of phosphoramidite as O-phosphitylation agent and its reactivity
-
O-phosphorylated peptide and amino acid are important in living system. In this paper, Dialkyl-N,N-dialkyl phosphoramidites (DDPA) 3 were synthesized using two methods. The reaction of DDPA with the hydroxyl group of the corresponding amino acids in the presence of tetrazole, followed by oxidation, gave O-phosphoryl amino acid methyl esters in a good yield. A systematical study of the reactivity of DDPA was presented too.
- Chen, Shui-Bing,Li, Yan-Mei,Luo, Shi-Zhong,Zhao, Gang,Tan, Bo,Zhao, Yu-Fen
-
p. 277 - 291
(2007/10/03)
-
- Carbocyclic analogues of D-ribose-5-phosphate: Synthesis and behavior with 5-phosphoribosyl α-1-pyrophosphate synthetases
-
The synthesis of cyclopentyl and cyclopentenyl analogues of the α- anomer of D-ribose-5-phosphate from D-ribonolactone and D-ribose is described. These analogues, which have the same absolute configuration as D- ribose-5-phosphate, were incubated with PRPP synthetases in an attempt to prepare the corresponding carbocyclic PRPP analogues. The carbocyclic ribose- 5-phosphate analogues were found to be inhibitors, rather than substrates, for 5-phosphoribosyl α-1-pyrophosphate synthetases of both bacterial and human origin. The inhibitory behavior of the analogues is described.
- Parry, Ronald J.,Burns, Mark R.,Skae, Phillip N.,Hoyt, Jeffrey C.,Pal, Biman
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p. 1077 - 1088
(2007/10/03)
-
- synthesis and Solid-State Structure of Substituted Arylphosphine Oxides
-
We described the preparation and characterization of several new arylphosphine oxides, which are of interest as second-order nonlinear optical materials. (4-Aminophenyl)diphenylphosphine oxide (1a), bis(4-aminophenyl)phenylphosphine oxide (2a), and (4-aminophenyl)bisphosphine oxide (5) were prepared by addition of aryl Grignard and organolithium reagents containing protected amines to phosphorus oxyhalides.Alternatively, 1a was prepared by treatment of (4-bromophenyl)diphenylphosphine oxide with azidomethyl phenyl sulfide, followed by hydrolysis. (4-Aminophenyl)(4'-nitrophenyl)phenylphosphine oxide (6) was prepared by nucleophilic aromatic substitution of bis(4-fluorophenyl)phenylphosphine oxide to give the corresponding dinitro compound, followed by selective mono-reduction.The X-ray crystal structure of (4-aminophenyl)diphenylphosphine oxide (1a), along with those of mono-, di-, and trihydroxy triphenylphosphine oxides 1b, 2b, and 3b, exhibit extensive intermolecular hydrogen bonding.The hydrogen bonding in 1a and 1b produces chains of arylphosphine oxide molecules with a head-to-tail alignment; the chains pack in an antiparallel manner to produce solid-state structures that display only slight deviations from centrosymmetry.
- Whitaker, Craig M.,Kott, Kevin L.,McMahon, Robert J.
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p. 3499 - 3508
(2007/10/02)
-
- Use of Bis N,N-Dialkylphosphoramidites for the Synthesis of Phosphate Monoesters
-
The bis N,N-dialkylphosphoramidites 7a and b and bis N,N-dialkylphosphoramidites 6a and b have been prepared by reaction of the N,N-dialkylphosphorochloridites 5a and b with the appropriate 2-(trialkylsilyl)ethanol.In the presence of 1H-tetrazole, the phosphoramidites 6a, b and 7a, b phosphorylated MeOH, PhCH2OH, PhCH2CH2OH, Me(PhCH2CH2(CHOH, 2,3,4,5,6-penta-O-benzyl-myo-inositol and ButOH, to give the phosphites 8a-h.Without isolation, these were oxidized to the corresponding phosphate triesters 9a-h with m-chloroperbenzoic acid.Treatment of the triesters 9a-h with tetrabutylammonium fluoride removes only 2-(trialkylsilyl)ethyl group to give the diesters 10a-h, whereas treatment with a solution of hydrofluoric acid in acetonitrile-water gives the phosphate monoesters 11a-e.
- Ross, Kenneth C.,Rathbone, Daniel L.,Thompson, William,Freeman, Sally
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p. 421 - 426
(2007/10/02)
-
- FEATURES OF THE REACTION OF N-BENZOYL- AND N-PHOSPHINOYL-TRIFLUOROACETIMIDOYL CHLORIDES WITH PHOSPHORUS(III) AMIDES
-
Reaction of N-substituted trifluoroacetimidoyl chlorides CF3C(Cl)=NX with P(III) amides leads to aminophosphonium salts CF3C+(NR2)3>=NX Cl-, which are stable in the solid state and decompose in solvents of low polarity to give amidines CF3C(NR2)=NX and aminochlorophosphines (R2N)nPCl(3-n).The stability of these salts decreases in the following series of X: PhC(O) > Cl2P(O) > (EtO)2P(O), and of R: Et > Me; and increases with increase in solvent polarity.Reaction of imidoyl chlorides with o-phenylene diethylphosphoramidite depends on the nature of the N-substituent: with X = PhC(O) -cycloaddition is realized, leading to spirophosphoranes, while with X = P(O)Cl2 or P(O)(OEt)2 amination occurs, leading to formation of amidines and aminochlorophosphines.In the reactions of imidoyl chlorides with Ph3P the phosphorane Ph3PF2 was detected, which was probably formed via halogenophilic attack.
- Onys'ko, P. P.,Kolodka, T. V.,Kolotilo, N. V.,Kudryavtsev, A. A.,Sinitsa, A. D.
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p. 359 - 364
(2007/10/02)
-
- An improved synthesis of dihydroxyacetone phosphate
-
An improved procedure has been developed for the synthesis of dihydroxyacetone phosphate (DHAP). Reaction of 2,5-diethoxy-p-dioxane-2,5-dimethanol (1) and the trivalent phosphorylating reagent dibenzyl-N,N-diethylphosphoramidite (DDP) in the presence of 1,2,4-triazole or tetrazole followed by oxidation with H2O2 gave 2,5-diethoxy-p-dioxane-2,5-dimethanol-O-21-O-51-bis(phosphate) tetrabenzyl ester (2) in 98% yield. Compound 2 was then hydrogenated in the presence of H2-Pd/C to give, after neutralization, 2,5-diethoxy-p-dioxane-2,5-dimethanol-O-21-O-51-bis(phosphate) as a stable trisodium salt (3) in 84% yield. Treatment of 3 with Dowex 50 (H+) generates 2 equivalents of DHAP.
- Pederson,Esker,Wong
-
p. 2643 - 2648
(2007/10/02)
-
- PREPARATION AND REACTIONS OF METHYLTHIOMETHYL-SUBSTITUTED PHOSPHORUS HALIDES
-
Methylthiomethylphosphonous dichloride, MeSCH2PCl2 (1), is synthesized by the reaction of MeSCH2SnBun, with phosphorus trichloride.Substitution reactions to give MeSCH2PX2 (X = NEt2, OPri, F, Ph) are described.The phosphorus(III) compounds are readily converted to the corresponding phosphonyl and thiophosphonyl derivatives, MeSCH2P(Z)X2 (Z = O, S), and the phosphorane, MeSCH2PF4, respectively.Chlorination of the methylene group to give compounds of the type MeSCHClP(O)X2 and MeSCCl2P(O)X2 is reported.Key words: Methylthiomethylphosphorus compounds; phosphorus halides; carbon-tin cleavage
- Fild, M.,Vahldiek, M.
-
p. 207 - 214
(2007/10/02)
-
- Di-tert-butyl N,N-Diethylphosphoramidite. A New Phosphitylating Agent for the Efficient Phosphorylation of Alcohols
-
Alkyl and aryl di-tert-butyl phosphates were prepared in high yields by the 1H-tetrazole-promoted phosphitylation of alkyl and aryl alcohols with di-tert-butyl N,N-diethylphosphoramidite, followed by oxidation of the resultant alkyl and aryl di-tert-butyl
- Perich, John W.,Johns, R. B.
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p. 142 - 144
(2007/10/02)
-
- ZUR KENNTNIS DER ORGANOPHOSPHORVERBINDUNGEN XX. Bifunktionelle Aminophosphane (Et2N)2P-n-P(NEt2)2 und Et2N(R)P-n-P(R)NEt2
-
Bifunctional aminophosphanes (Et2N)2P-n-P(NEt2)2 (n = 1-10) (1) and Et2NP(R)-n-P(R)NEt2 (n = 2-4, R = Alkyl, Ph) (2), which are valuable intermediates in organophosphorus synthesis, are obtained by two methods.Because of the marked nucleophility of phosphorus in 1 and 2, reactions with Lewis acids take place very smoothly as is shown by preparation of (Et2N)2P(X)-4-(X)P(NEt2)2 (X = O, S, Se, Te, BH3, BBr3) and 4-(CH3)P(NEt2)2>2+2I-.Fission of P-N bonds by PCl3, MeOH, H2S and CS2 affords Cl2P-4-PCl2, (MeO)2P-4-P(OMe)2, (MeO)Et2NP-4-PNEt2(OMe), the dithiophosphinate 4-(H)PS2>2-2 Et2NH2+, and the dithiocarbaminate 2P-4-P2.The 31P/1H/NMR-Spectra are discussed especially with regard to steric aspects in the synthesis of the chiral compounds 2 and their derivatives.
- Diemert, Klaus,Kuchen, Wilhelm,Kutter, Juergen
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p. 155 - 164
(2007/10/02)
-
- A New Synthesis of Organodifluorophosphites and their Reaction with Platinum(II) Complexes
-
Alkyldifluorophosphites, ROPF2 (R = p-substituted benzyl group, neopentyl, 1-adamantyl) have been obtained by a new method, involving reaction of the appropriate alkyl trimethylsilylether, ROSiMe3 with chlorodifluorophosphine, PF2Cl.Reactions of these dif
- Krueger, Wieland,Sell, Michael,Schmutzler, Reinhard
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p. 1074 - 1080
(2007/10/02)
-
- SUBSTITUTION OF THE ANION IN AMMONIUM AND PHOSPHONIUM CHLORIDES BY THE ACTION OF ELECTROPHILIC AGENTS
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N,N-Dialkylmethaniminium iodides were obtained by the reactions of N,N-dialkylmethaniminium chlorides with methyl iodide.The reactions of ammonium and phosphonium chlorides with triethyloxonium tetrafluoroborate, dimethyl sulfate, methyl tosylate, and methyl iodide take place with substitution of the chloride ion by the BF4-, CH3SO3O-, p-CH3C6H4SO3- or I- ions.Substitution of the chloride ion of phosphonium salts by the iodide ion can be realized by the action of trimethyliodosilane.
- Kukhar', V. P.,Pasternak, V. I.,Shevchenko, I. V.,Shevchenko, M. V.,Marchenko, A. P.,Makovetskii, Yu. P.
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p. 161 - 166
(2007/10/02)
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- SOME EXCHANGE REACTION IN THE SERIES OF THIODERIVATIVE ACIDS OF TRIVALENT PHOPHORUS
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1.It was shown that reactions of thioesters of acids of trivalent phosphorus with PIII acid halides proceed with substitution of the thioalkyl groups. 2.Thiosphosphorous acid chlorides interact readily with aminophosphites, leading to products of exchange of chlorine atoms for amide groups.
- Sinyashin, O. G.,Ofitserov, E. N.,Batyeva, E. S.,Pudovik, A. N.
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p. 2078 - 2080
(2007/10/02)
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- PHOSPHORORGANISCHE VERBINDUNGEN 93 Zur Chemie optisch aktiver Phosphinigsaereamide
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Optically active ethyl-phenyl-phosphinous acid diethylamide 1 was treated with HCl, HBF4, alcohols, thiols, carboxylic acids, esters, anhydrides, acid chloride, compounds with the structure element P-Cl and secondary phosphines to give in each case a racemic mixture of the corresponding, previously described, reaction products.Reaction of optically active 1 with para-cresol, para-cresyltrifluoro-acetate or 2,2,2-trifluoro-ethyl-trifluoro-acetate gives the corresponding optically active ester of ethyl phenyl phosphinous acid under retention of configuration.
- Horner, Leopold,Jordan, Manfred
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p. 235 - 242
(2007/10/02)
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- NMR study (1H, 13C and 31P) of the nPX3-n compounds (X=Cl, C2H5; n=0,1,2,3)
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1H, 13C and 31P NMR data of the compounds nPX3-n (X=Cl, C2H5; n=0,1,2,3) are reported.While the 1H and 13C resonances from the PEt moiety rather follow the electron-withdrawing effect of the -NEt substituent, 1H and 13C chemical shift data from the -NEt2 moiety reveal a quite important shift contribution originating from sterically induced polarization of the C-H bonds. 31P chemical shift data are interpreted in terms of inductive effects but the anomalous diamagnetic shift deviation from linearity for X=Cl suggests a minor contribution from multiple bonding.The general trend observed in the 31P-couplings is quite straightforward and can be qualitatively explained by Bent's rule.
- Linthoudt, J. P. van,Berghe, E. V. van den,Kelen, G. P. van der
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p. 315 - 320
(2007/10/02)
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