Addition Reactions of Esters of Phosphorus(III) Acids with Unsaturated Systems

Pudovik, A. N.; Konovalova, I. V.

doi:10.1055/s-1979-28566

Cited by 322 publications

(169 citation statements)

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“…[37,38] As shown in Scheme 2, the α-hydroxymethylene phosphonate 7 was prepared by the addition of aldehyde 6 to dimethylphosphite in the presence of triethylamine. This addition reaction occurred non-stereospecifically, as two single sharp resonances of equal intensity at δ = 25.37 and 24.47 ppm were observed in the 31 P NMR spectrum.…”

Section: Chemical Synthesismentioning

confidence: 99%

α‐Substituted Phosphonate Analogues of Lysophosphatidic Acid (LPA) Selectively Inhibit Production and Action of LPA

Jiang

Fujiwara

et al. 2007

ChemMedChem

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Isoform-selective agonists and antagonists of the lysophosphatidic acid (LPA) G-protein-coupled receptors (GPCRs) have important potential applications in cell biology and therapy. LPA GPCRs regulate cancer cell proliferation, invasion, angiogenesis, and biochemical resistance to chemotherapy-and radiotherapy-induced apoptosis. LPA and its analogues are also feedback inhibitors of the enzyme lysophospholipase D (lysoPLD, also known as autotaxin), a central regulator of invasion and metastasis. For cancer therapy, the ideal therapeutic profile would be a metabolically stabilized pan-LPA receptor antagonist that also inhibits lysoPLD. Herein we describe the synthesis of a series of novel α-substituted methylene phosphonate analogues of LPA. Each of these analogues contains a hydrolysis-resistant phosphonate mimic of the labile monophosphate of natural LPA. The pharmacological properties of these phosphono-LPA analogues were characterized in terms of LPA receptor subtype-specific agonist and antagonist activity using Ca 2+ mobilization assays in RH7777 and CHO cells expressing the individual LPA GPCRs. In particular, the methylene phosphonate LPA analogue is a selective LPA 2 agonist, whereas the corresponding α-hydroxymethylene phosphonate is a selective LPA 3 agonist. Most importantly, the α-bromomethylene and α-chloromethylene phosphonates show pan-LPA receptor subtype antagonist activity. The α-bromomethylene phosphonates are the first reported antagonists for the LPA 4 GPCR. Each of the α-substituted methylene phosphonates inhibits lysoPLD, with the unsubstituted methylene phosphonate showing the most potent inhibition. Finally, unlike many LPA analogues, none of these compounds activate the intracellular LPA receptor PPARγ.

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Section: Chemical Synthesismentioning

confidence: 99%

α‐Substituted Phosphonate Analogues of Lysophosphatidic Acid (LPA) Selectively Inhibit Production and Action of LPA

Jiang

Fujiwara

et al. 2007

ChemMedChem

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“…Hence, the Pudovik reaction gives rise to the formation of a-aminophosphonates if an imine is employed as p-system. [11] Continuous efforts are being made to improve the synthesis of a-aminophosphonates [12] and recent advances of the Kabachnik-Fields and the Pudovik reactions comprise stereoselective [13] and catalytic enantio-selective [14,15] syntheses as well as the use of microwave techniques. [16] Selective activation of CA C H T U N G T R E N N U N G (sp 3 ) À H bonds for subsequent cross-coupling reactions is an attractive concept that has strongly developed during the last decade because it removes the need for reactant prefunctionalization.…”

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confidence: 99%

Iron‐Catalyzed Oxidative Mono‐ and Bis‐Phosphonation of N,N‐Dialkylanilines

2010

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Abstract:The dehydrogenative a-phosphonation of substituted N,N-dialkylanilines by dialkyl H-phosphonates was achieved under mild conditions by using environmentally benign iron(II) chloride as catalyst and tert-butyl hydroperoxide as oxidant. The reaction proceeded in the presence of electron-donating (methoxy, methyl, benzyl) and electron-withdrawing ring-substitutents (bromo, carbonyl, carboxyl, m-nitro) in moderate to good yields. The X-ray crystal structure of N-(5,5-dimethyl-2-oxo-2l 5 -[1,3,2]dioxaphosphinan-2-yl-methyl)-N-methyl-p-toluidine was determined. Bis-(4-(dimethylamino)phenyl)methane and bis-4,4'-(dimethylamino)benzophenone underwent bisphosphonation selectively by respective monophosphonation at the remote dimethylamino groups. Furthermore, the use of excess di-

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“…In THF solution this equilibrium is shifted even more towards 1 B: in the 31 P NMR spectrum only the resonance of the pentavalent tautomer 1 B was observed [ 31 P NMR (162 MHz, CD 2 Cl 2 , 258C): d = 11.3 ppm]. [15,16] The structure of the pentavalent tautomer 1 B was unambiguously proven by X-ray structure analysis.…”

Section: Resultsmentioning

confidence: 99%

Heteroatom‐Substituted Secondary Phosphine Oxides (HASPOs) as Decomposition Products and Preligands in Rhodium‐Catalysed Hydroformylation

Christiansen

Selent

Spannenberg

et al. 2011

Chemistry A European J

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O,O'-3,3'-Di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl phosphonate (1) is the hydrolysis product of several mono- and bis-phosphites used as ligands in industrial hydroformylation and other catalytic reactions. As a result of a tautomeric equilibrium, this pentavalent heteroatom-substituted phosphine oxide (HASPO) can rearrange to the corresponding trivalent phosphorus compound. The latter is able to react with typical rhodium-containing precursors frequently used for the generation of catalysts. The resulting species were characterised by NMR spectroscopy and X-ray structure analysis. Proof is given that a rhodium complex of 1 forms an active hydroformylation catalyst. Moreover, 1 can add to aldehydes, which are generated as products in the hydroformylation. Thus a broad range of subsequent reactions can be associated with the degradation of the original phosphite ligands, which has a strong influence on the overall outcome of the hydroformylation reaction.

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Addition Reactions of Esters of Phosphorus(III) Acids with Unsaturated Systems

Cited by 322 publications

References 0 publications

α‐Substituted Phosphonate Analogues of Lysophosphatidic Acid (LPA) Selectively Inhibit Production and Action of LPA

α‐Substituted Phosphonate Analogues of Lysophosphatidic Acid (LPA) Selectively Inhibit Production and Action of LPA

Iron‐Catalyzed Oxidative Mono‐ and Bis‐Phosphonation of N,N‐Dialkylanilines

Heteroatom‐Substituted Secondary Phosphine Oxides (HASPOs) as Decomposition Products and Preligands in Rhodium‐Catalysed Hydroformylation

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