- One-pot synthesis of 1-hydroxymethylene-1,1-bisphosphonate partial esters
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A selective one-pot procedure of synthesis of 1-hydroxymethylene-1,1- bisphosphonic partial trimethylesters and P,P-, P,P′-diesters was described.
- Migianu, Evelyne,Mallard, Isabelle,Bouchemal, Nadia,Lecouvey, Marc
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Read Online
- Phosphorus compounds as photoinitiators for radicalic polymerization
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p-Methoxybenzoyldialkylphosphonates, where alkyl = methyl, ethyl and p-methoxy-benzoyldiphenylphosphine oxide were synthesized by Michaelis-Arbuzov reaction. These compounds were used as photoinitiators for radicalic polymerization of acrylic monomers. Th
- Macarie, Lavinia,Ilia,Iliescu, Smaranda,Popa, Adriana,Dehelean,Manoviciu,Petrean,Abadie
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p. 165/[421]-173/[429]
(2004)
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Read Online
- One-pot synthesis of phosphinylphosphonate derivatives and their anti-tumor evaluations
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This paper reports on the synthesis of new hydroxymethylene-(phosphinyl)phosphonates (HMPPs). A methodology has been developed to propose an optimized one-pot procedure without any intermediate purifications. Various aliphatic and (hetero)aromatic HMPPs were synthesized in good to excellent yields (53–98%) and the influence of electron withdrawing/donating group substitution on aromatic substrates was studied. In addition, the one-pot synthesis of HMPP was monitored by31P NMR spectroscopy, allowing effective control of the end of the reaction and identification of all phosphorylated intermediate species, which enabled us to propose a reaction mechanism. Optimized experimental conditions were applied to the preparation of biological relevant aminoalkyl-HMPPs. A preliminary study of the complexation to hydroxyapatite (bone matrix) was carried out in order to verify its lower affinity towards bone compared to bisphosphonate molecules. Moreover, in vitro anti-tumor activity study revealed encouraging antiproliferative activities on three human cancer cell lines (breast, pancreas and lung).
- Deschamp, Julia,Dussart-Gautheret, Jade,Lecouvey, Marc,Legigan, Thibaut,Migianu-Griffoni, Evelyne,Monteil, Maelle
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- Selective P?C(sp3) Bond Cleavage and Radical Alkynylation of α-Phosphorus Alcohols by Photoredox Catalysis
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Herein the first P?C(sp3) bond cleavage and radical alkynylation of α-phosphorus alcohols to construct phosphonoalkynes is reported. The phosphorus radical is generated upon P?C bond cleavage reaction via the alkoxyl radical through photoredox catalysis with cyclic iodine(III) reagents. Various arylphosphinoyl-, alkylphosphinoyl-, phosphonate-, and phosphonic amide alcohols serve as radical phosphorus precursors to construct phosphonoalkynes for the first time.
- Jia, Kunfang,Li, Junzhao,Chen, Yiyun
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supporting information
p. 3174 - 3177
(2018/02/09)
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- Geminal difunctionalization of α-diazo arylmethylphosphonates: Synthesis of fluorinated phosphonates
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A general approach towards diverse fluorinated phosphonates via geminal difunctionalization reactions of α-diazo arylmethylphosphonates is described. The diazo functionality (RR′CN2) is successfully converted to RR′CF2, RR′CHF, RR′CFBr or RR′CFNR′′2 groups by employing different fluorination reagents. A variety of fluorinated organophosphorus compounds were readily accessed in good to excellent yields from a common type of precursor.
- Zhou, Yujing,Zhang, Yan,Wang, Jianbo
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p. 10444 - 10453
(2016/11/18)
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- Reactions of acyl phosphonates with organoaluminum reagents: A new method for the synthesis of secondary and tertiary α-hydroxy phosphonates
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The reactions of organoaluminum reagents (trimethylaluminum, triethylaluminum, etc.) with aryl and alkyl acyl phosphonates, which lead to the formation of α-hydroxy phosphonates in moderate to good yields, are reported. This method provides easy access to
- Seven, Ozlem,Polat-Cakir, Sidika,Hossain, Md. Shakhawoat,Emrullahoglu, Mustafa,Demir, Ayhan S.
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body text
p. 3464 - 3469
(2011/06/19)
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- Asymmetrie hydrogenation of α,ss-unsaturated esterphosphonates
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The rhodium-catalyzed asymmetric hydrogenation of readily available α,ss-unsaturated esterphosphonates affords the corresponding α-chiral phosphonates in excellent yield and ee. The resulting products are useful multifunctional building blocks applied in
- Huang, Yange,Berthiol, Florian,Stegink, Bart,Pollard, Michael M.,Minnaard, Adriaan J.
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experimental part
p. 1423 - 1430
(2009/12/24)
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- New efficient synthesis of 1-hydroxymethylene-1,1-bisphosphonate monomethyl esters
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A new efficient procedure for the synthesis of 1-hydroxymethylene-1,1- bisphosphonate monomethyl esters in three steps from acid chlorides is reported here. Georg Thieme Verlag Stuttgart.
- Migianu, Evelyne,Guénin, Erwann,Lecouvey, Marc
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p. 425 - 428
(2007/10/03)
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- Lanthanide complexes of new nonadentate imino-phosphonate ligands derived from 1,4,7-triazacyclononane: Synthesis, structural characterisation and NMR studies
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The polyamino ligand 1,4,7-tris(2-aminoethyl)-1,4,7-triazacyclononane (1) has been used to synthesise two new ligands by Schiff-base condensation with methyl sodium acetyl phosphonate to give ligand L and methyl sodium 4-methoxybenzoyl phosphonate to give
- Tei, Lorenzo,Blake, Alexander J.,Wilson, Claire,Schroeder, Martin
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p. 1945 - 1952
(2007/10/03)
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- The Schmidt reaction of dialkyl acylphosphonates
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The scope of the Schmidt rearrangement of ketones has been extended to dialkyl acylphosphonates (11a-11l). Surprisingly, it was found that 11a-11d and 11g, in which the acyl moiety was benzoyl alone or benzoyl bearing an electron-attracting or mildly electron-releasing substituent, yielded an overwhelming portion of products resulting from C-to-N migration of the aryl group (N-arylcarbamoylphosphonates, 12, and N-arylformamides, 15). Contrariwise, the arenecarbonylphosphonates, which carry a powerful electron-releasing p-alkoxy group, yielded products resulting from phosphonate group migration from C to N or elimination (dialkyl N-arenecarbonylphosphoramidates, 13, and arenecarbonitriles, 17, respectively). These counterintuitive results are rationalized by application of the concept of "degree of electron demand" to this area of intramolecular rearrangements. The possible existence of an additional pathway for the Schmidt rearrangement, involving protonation of the iminodiazonium ion, is proposed.
- Sprecher, Milon,Kost, Daniel
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p. 1016 - 1026
(2007/10/02)
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- Novel Quasiphosphonium Ylides from the Reaction of Trialkyl Phosphites with Dialkyl Benzoylphosphonates: Evidence for Carbene Intermediates in the Intramolecular Cyclisation of 2-Substituted Dialkyl Benzoylphosphonates
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The reaction of dialkyl aroylphosphonates 1 with trialkyl phosphites leads to the formation of novel quasiphosphonium ylides 4 which in some cases thermally rearrange to the bisphosphonates 5. 2-Substituted dialkyl aroylphosphonates may also undergo intra
- Griffiths, D. Vaughan,Griffiths, Penelope A.,Whitehead, Belinda J.,Tebby, John C.
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p. 479 - 484
(2007/10/02)
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- α-OXYIMINOPHOSPHONATES: CHEMICAL AND PHYSICAL PROPERTIES. REACTIONS, THEORETICAL CALCULATIONS, AND X-RAY CRYSTAL STRUCTURES OF (E) AND (Z)-DIMETHYL α-HYDROXYIMINOBENZYLPHOSPHONATES
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Dialkyl α-oxyiminoalkylphosphonates, obtained by treatment of dialkyl acylphosphonates with hydroxylamine or methoxylamine, are mostly mixtures of E and Z isomers.Structural assignments of the oximes were based on X-ray crystallographic analysis of representative compounds: (E)- and (Z)-dimethyl α-hydroxyiminobenzylphosphonates .The (31)P n.m.r. chemical shifts of the E isomers always appear at lower field than those of the corresponding Z isomers.Thermal fragmentation of (1a) affords benzonitrile and dimethyl hydrogen phosphate, with (Z)-(1a) reacting faster than the E isomer. α-Oxyiminophosphonates undergo EZ isomerisation catalysed either by acid or by base under certain conditions, the E isomer being the thermodinamically more stable one.An E + Z mixture of dialkyl α-oxyiminophosphonates can be mono-de-alkylated by non-basic nucleophiles (e.g.NaI) to afford monoalkyl oxyiminophosphonates of unchanged isomeric composition.The geometrical isomers of α-hydroxyiminophosphonates differ in their behaviour under basic conditions.While treatment of (E)-(1a) with NaOH in boiling methanol leads, by mono-de-alkylation, to sodium methyl α-hydroxyiminobenzylphosphonate , under the same conditions (Z)-(1a) undergoes fragmentation, by C-P bond cleavage, to benzonitrile and dimethyl hydrogen phosphate.Control experiments established that the fragmentation of (Z)-α-hydroxyiminophosphonates involves an intramolecular attack on the phosphorous atom by the ionized Z oriented oxime oxygen.Similar differences in behaviour are noted between the isomers of the monoanions of α-hydroxyiminophosphonates.MNDO/H Calculations demonstrate the feasibility of forming internal hydrogen bonds in Z isomers, and their possible contribution to conformational preferences.Single-crystal X-ray diffraction studies of (E)- and (Z)-(1a), and (E)-(2b), clearly identified the geometric isomers and correlated them with (1H) and (31)P n.m.r. resonances.
- Breuer,Eli,Karaman, Rafik,Goldblum, Amiram,Gibson, Dan,Leader, Haim,et. al.
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p. 3047 - 3058
(2007/10/02)
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