Phosphorylation diphosphorylation

O Phosphorylation of the tertiary hydroxyl and diphosphorylation of the primary hydroxyl, followed by decarboxylation and simultaneous expulsion of phosphate, gives isopentenyl diphosphate, the precursor of terpenoids,... 

In contrast, synthesis of 3,4-diphosphorylthiophenes requires more elaboration because of low reactivity of 3,4-positions of thiophene and unavailability of 3,4-dihalo or dimetallated thiophenes. Minami et al. synthesized 3,4-diphosphoryl thiophenes 16 as shown in Scheme 24 [46], Bis(phosphoryl)butadiene 17 was synthesized from 2-butyne-l,4-diol. Double addition of sodium sulfide to 17 gave tetrahydrothiophene 18. Oxidation of 18 to the corresponding sulfoxide 19 followed by dehydration gave dihydrothiophene 20. Final oxidation of 20 afforded 3,4-diphosphorylthiophene 16. 3,4-Diphosphorylthiophene derivative 21 was also synthesized by Pd catalyzed phosphorylation of 2,5-disubstituted-3,4-dihalothiophene and converted to diphosphine ligand for Rh catalysts for asymmetric hydrogenation (Scheme 25) [47],... 

Phosphoryl radicals [10, 18, 38-42] tend to add to double bonds. Owing to the exceptionally high constants of hyperfine coupling of the unpaired electron with the phosphorus nucleus, phosphoryl radicals can be utilized as paramagnetic reporters [10]. Phosphoryl radicals have been prepared by photolysis of diphosphoryl mercury compounds (Scheme 6.5). 

The authors experience is that the enzymic phosphorylation and diphosphorylation of nucleoside monophosphates is very efficient the yields are nearly quantitative and the immobilized enzyme system appears reusable for at least three months. 

The phosphorylation of potassiopyrrole by the chlorides of phosphorous acid shows [21] that the process is selective and leads to the products from N-phosphorylation. The reaction of 2,4-dimethyl- and 2,3,5-trimethylpyrroles with chlorophosphites makes it possible to obtain mono- and diphosphorylated alkylpyrroles, depending on the ratio of the phosphorylating agent and alkylpyrrole [22, 23]. 

In reaction with amidophosphites hydroxymethylindole 80a gives the N-phosphorylation (80) and O-phosphorylation (81) products [77], At -5°C compound 80 is formed preferentially (80-85%) if the temperature is raised to 80°C its fraction amounts to 65-70%, while that of the O-phosphorylation product 81 is 30-35%. With a twofold excess of the amidophosphite instead of equimolar amount it is possible to obtain the diphosphorylated derivatives of 3-methylindole (82). All the compounds with a tricoordinated phosphorus atom (80-82) are easily oxidized in air to the corresponding compounds with a tetracoordinated phosphorus atom (83-85) ... 

Hydroxy-morpholino-phosphoryl)- XII/2, 402 5 -0-(Hydroxy-phenoxy-diphosphoryl)- XII/2, 888 5 -0-(Hydroxy-phenoxy-phosphoryl)-2, 3 -0-iso-propyliden- XII/2, 233... 

With phosphoryl chloride in alkali, imidazole gives the diphosphoryl imidazole (71) while 1-methylimidazole gives an analogous product. Such iV-phosphorylimidazoles play an important role in enzymic transphosphorylation. When two moles of imidazole (or benzimidazole) react with one mole of dialkyl (or diaryl) phosphoric acid chloride, the compounds (72) are formed, and di- and tri-imidazolides of phosphoric acid (e.g. 73) can be obtained similarly from phosphoric acid dichloride or from phosphoryl chloride (Scheme... 

For HSV at least three mechanisms have been described that generate resistance to AC V deficiency or loss of viral TK activity, alteration in substrate specificity of the virus-encoded TK, and alteration in the substrate specificity of the viral DNA polymerase (1,8). Most of the ACVr mutants that have been isolated in vitro and recovered from clinical specimens are TK-deficient (TK). However, resistant clinical mutants that have an altered TK or altered DNA polymerase activity have occasionally been described too. Although TK mutants are crossresistant with drugs that also depend on viral TK for their activation (i.e., GCV, penciclovir and brivudin (BVDU), they remain sensitive to agents, such as PFA, vidarabine (Ara-A), and the acyclic nucleoside phosphonate (ANP) analogs. PFA, a pyrophosphate analog, is a direct inhibitor of the viral DNA poly-merase in which it binds to the site involved in releasing the pyrophosphate product of DNA synthesis. Phosphorylation of Ara-A to Ara-A triphosphate is carried out by cellular enzymes phosphorylation of ANP derivatives to their mono- and diphosphoryl derivatives is also carried out by cellular enzymes. 

Phosphorus-containing enamines have been prepared by phosphorylation of N-vinyl substituted tertiary amides, lactams and cyclic imides with phosphorus pentachloride ". Addition of amines to diphosphoryl alkynes has been described. Addition of RR NH [R = H, Ri = Me, cyclohexyl, PhCH2 RR = (CHj) to (Et0)2P(0)C=CP(0K0Et2)2 in CH2CI2 at 25 °C gave 93-100% of (Et0)2P(0)C(NRRi)=CHP(0)(0Et2)2 . Speziale and coworkers have studied the reactions of phosphorus compounds with trichloroacetamides. 

The rate of phosphorylation is greater than the estimated rate of dephosphorylation, 0.25 s (Kamm and Stull, 1985b). Measurements of nonphosphory-lated, monophosphorylated, and diphosphorylated forms of myosin in tracheal smooth muscle tissue provide direct evidence that myosin RLC phosphorylation occurs as a random rather than an ordered or cooperative phosphorylation process (Persechini etal., 1986). These results are consistent with biochemical measurements (Sellers et al., 1983 Trybus and Lowey,... 

Figure 8 Analysis of phosphorylation kinetics by time-resolved ESI-TOF-MS. (a) FGFR1 autophosphorylation. A selection of MS spectra collected by time-resolved ESI-TOI MS showing the formation of mono and diphosphorylated FGFR1 species at increasing reaction times. OP, 1P, and 2P represent the FGFR1 in unphosphorylated, mono, and diphosphoryl states.

Pyrolysis (at just above the melting point) of the distally diphosphorylated compound (9), and of the proximal diphosphate (10), and also of the tetraphos-phate, as well as of other compounds such as the trichloride (13), afforded the pyrophosphate (17), the structure of which was also confirmed by X-ray diffraction. The pyrolysis of partially phosphorylated derivatives of the terr-butyl-calix[6]arene also gave the bisbicyclic phosphate (16). ... 

On the basis of their differences in isoelectric point (pi), phosphorylated proteins can be separated in capillary isoelectric focusing (CIEF). Wei et al. employed a CIEF method using a capillary covalently coated with linear polyacrylamide and a pH gradient from 4 to 6.5 for the resolution of mono- and diphosphorylated ovalbumins. Proteins were detected by their UV absorbance at 280 nm. Additional ovalbumin variants within each of the mono- and diphosphoovalbumins, differing in their amount of glycosylation, were further analyzed by online CIEF-electrospray ionization (ESI)-MS. 

Previously the possibility of using Sc, Sm, and Nd mono- and diphosphorylated amines 1-3 as membrane carriers in conditions of active transport with use of 1,2-dichlorobenzene as a membrane solvent has been shown. At the same time, a high rate of transmembrane transfer of ions Sc and Nd N,N-bis(dihexyl phosphoryl methyl) octyl amine (1) was set. In this paper, the new results of research of membrane transport properties of 1-3 carriers, by symport mechanism are described, and in this case the environmentally acceptable solvent—kerosene as a membrane phase was used. Besides that the membrane-transport properties of diphosphorilamine 4, that have not been described previously containing simultaneously highly lipophilic methyl dioctyl phosphorylic and practically hydrophilic 0,0-diethyl ethyl phosphonate groups in a molecule was studied. It is well-known that creation of optimal hydrophilic-lipophilic balance is a precondition of transmembrane transport effectiveness with organophosphorous carriers. ... 

Cd, C, and P NMR to monitor the disposition, occupancy, and role of the individual metal binding sites in substrate phosphate binding and serine phosphorylation. Specifically, these studies showed that substrate binding and phosphorylation requires a minimum occupancy of the A and B site on a monomer. Thus, while the first two equivalents of Cd added bind to the symmetric A sites on each monomer, addition of phosphate results in the relocation of the metal ions to give a distribution where 50% are apo monomers and 50% are di-metal monomers. This is the chemical explanation for the elusive half of the sites reactivity and negative cooperativity reported in some studies on this enzyme Further addition of metal to saturate the 3 sites/monomer results in a synunetric diphosphorylated dimer giving rise to the spectra shown in Figures 4 and 5. 

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