Of 2’-phosphorylated

Alkylidene-l,3-dithianes, acting as acyl synthons, can be prepared by the HWE reaction of 2-phosphorylated 1,3-dithianes with aldehydes (Equation 53) <1996SL875, 1997BSE891, 1998TL5425, 2002JOC1746>. 

The conformational behaviour of 2-phosphoryl-l,3-dioxanes and dithianes continues to be an area of interest. Molecular mechanics methods have been applied to 2-phosphoryl-l,3-dioxane (34), the corresponding dithiane (35) and 2-thiophosphoryl-l, 3-dithiane (36).15 The relative stabilities of the axial and equatorial conformers in each case vary due to a combination of differing 1,3-axial interactions and anomeric effects. The conformer calculated to be the most stable for (34) and (35) is the structure given in each case. In the case of (36) the isomers are estimated to be of... 

Many references to kinetic measurements may have already been covered earlier with other physical methods. These include studies on pseudorotation of stereoisomers of a 10-P-5 spirophosphorane, on the formation rate of acylpho-sphonate hemiketals, on the rate of decomposition of hydroperoxides formed by the oxidation of soya phosphatidylcholine, on the kinetics of the reaction of trimethyl phosphite with benzylidene acetophenones, calorimetric studies on the reaction kinetics of dithiophosphoric acid 0,0 -dialkyl esters with zinc oxide, " and the kinetics of selective dephosphorylation of 2 -phosphorylated and 2 -thiophosphorylated dinucleotides. 

Gross, H., and CostiseUa, B., a-Substituted phosphonates. Part 28. Synthesis of 2-phosphorylated 1,3-benzodioxoles, 1,3-benzoxathioles and 1,3-benzodithioles, Synthesis, 622, 1977. 

Cyhexatin [13121 -70-5], tricyclohexylhydroxystannane (147) (mp 195°C), rat oral 540 mg/kg, and fenbutatin oxide [13356-08-6], hexakis-(2-methyl-2-phenylpropyl)distannoxane (148) (mp 138°C), rat oral LD q 2630 mg/kg, are two novel tin acaricides used on deciduous fmits. They are inhibitors of oxidative phosphorylation. 

Sulflutamid or A/-ethylpetfluotoctanesulfonamide [4151 -50-2] CgF yS02NHC2H, is a slow-acting stomach poison used in baits for the control of ants and cockroaches. It acts as an uncoupler of oxidative phosphorylation. 

The importance of quinones with unsaturated side chains in respiratory, photosynthetic, blood-clotting, and oxidative phosphorylation processes has stimulated much research in synthetic methods. The important alkyl- or polyisoprenyltin reagents, eg, (71) or (72), illustrate significant conversions of 2,3-dimethoxy-5-methyl-l,4-ben2oquinone [605-94-7] (73) to 75% (74) [727-81-1] and 94% (75) [4370-61-0] (71—73). 

A good example of an affinity label for creatine kinase has been presented (35). This enzyme catalyzes the reversible transfer of a phosphoryl group from adenosine triphosphate [56-65-5] (17) to creatine [57-00-1] (18), leading to adenosine diphosphate [7584-99-8] (19) and phosphocreatine [67-07-2]... 

In view of the high price and other difficulties associated with the use of phosphoryl bromide, the transhalogenation of 2-chloro- and 2-chloro-4,6-dimethyl-pyrimidine (919) by treatment with inexpensive phosphorus tribromide to give their bromo analogues in >50% yield, assumes potential importance as a general method (67JCS(C)1204). 

The reaction of 2,2 -bipyrrole with orthoformic acid triethyl ester in the presence of phosphoryl chloride (POCI3) produced a compound which gave the H NMR spectrum 5. Which compound has been prepared ... 

FIGURE 19.24 A mechanism for the phosphoglycerate mutase reaction in rabbit muscle and in yeast. Zelda Rose of the Institute for Cancer Research in Philadelphia showed that the enzyme requires a small amount of 2,3-BPG to phosphorylate the histidine residue before the mechanism can proceed. Prior to her work, the role of the phosphohistidine in this mechanism was not understood. 

Oxidation of 2 molecules each of isocitrate, n-ketoglutarate, and malate yields 6 NADH Oxidation of 2 molecules of succinate yields 2 [FADHg] Oxidative phosphorylation (mitochondria) 2 NADH from glycolysis yield 1.5 ATP each if NADH is oxidized by glycerol-phosphate shuttle 2.5 ATP by malate-aspartate shuttle + 3 + 5... 

The quantum yield of photosynthesis, the amount of product formed per equivalent of light input, has traditionally been expressed as the ratio of COg fixed or Og evolved per quantum absorbed. At each reaction center, one photon or quantum yields one electron. Interestingly, an overall stoichiometry of one translocated into the thylakoid vesicle for each photon has also been observed. Two photons per center would allow a pair of electrons to flow from HgO to NADP (Figure 22.12), resulting in the formation of 1 NADPH and Og. If one ATP were formed for every 3 H translocated during photosynthetic electron transport, 1 ATP would be synthesized. More appropriately, 4 hv per center (8 quanta total) would drive the evolution of 1 Og, the reduction of 2 NADP, and the phosphorylation of 2 ATP. 

In 1949, Comforth showed that preparation of 2,5-disubstituted oxazoles was not limited to diaryloxazoles through condensation of aldehydes (benzaldehyde, n-hept-aldehyde) with a-hydroxy-amides (lactamide). The intermediate oxazolidone 13 were converted into oxazoles 14 on warming with phosphoryl chloride. ... 

Proceeding from 5 -0-acetylazauridine (80), a mixture of 2 - and 3 -monophosphates (81, 82) was prepared by phosphorylation with polyphosphoric acid, and these were converted into the 2, 3 -cyclic phosphate (83). From the 2, 3 -0-isopropylidene derivative of 3-methyl-6-azauridine the 5 -phosphate was prepared by treatment with cyanoethylphosphate and the corresponding diphosphate from its morpholidate through the action of phosphoric acid. ° Furthermore, a diribonucleoside phosphate (85) with a natural 3 -5 internucleotide linkage was prepared from 6-azauridine, The starting material for the preparation of such derivatives was 5 -0-acetyl-2 -0 -tetrahydro-pyranyluridine-3 -phosphate (84) which was condensed with di-G-acetylazauridine (86) or with 2b3 -0-isopropylidene-6-azauridine (76) with the aid of dicyclohexylcarbodiimide. ... 

Preparation of 6-azacytidine-5 -phosphate by direct phosphorylation with cyanoethylphosphate was not successful. The substance could be prepared, however, on ammonia treatment of 4-thio-6-azauridine-5 -phosphate which was obtained by phosphorylation of 2, 3 -isopropyl-iden-4 thio-6-azauridine with pyrophosphoryl chloride. From mor-pholidate of 6-azacytidine-5 -phosphate, 6-azacytidine-5 -diphosphate was prepared by the action of phosphoric acid. ... 

Good yields of pyrido[2,3-d]pyrimidiries (37) were also oblaiiied by the action of formamide on o-amino nitriles (36). Reduction of 2-amino-4,6-dimethylnicotinitrilc yields the 3-aminomcthyl compound (38). Acylation to the 3-aoylaminomethyl derivative (39), followed by cyolization, by means of heat or phosphoryl chloride, yielded the dihydropyrido[2,3-d]pyrimidines (40). ... 

A more complicated reaction sequence has been used by Ukita and Nagasawa (59) in their synthesis of 2-deoxy D-ribose 5-phosphate (2-deoxy D-erythro-pentose 5-(dihydrogen phosphate)), (29). They phosphorylated a mixture of the anomeric methyl deoxyribofuranosides (24)... 

In fact, it has been found (52) that in unbuffered solution, at room temperature, authentic 2-deoxy ribose 5-phosphate reduces more than 4 molar equivalents of periodate, but. that there is no noticeable slowing down of the reaction rate after the reduction of the first molar equivalent. This may be owing to the fact that only the aldehydo form (76) of 2-deoxy ribose 5-phosphate has a free vicinal diol group as the acyclic 2-deoxy ribitol 5-phosphate reduces one molar equivalent of periodate quite fast (58), it is probable that the time-curve of periodate uptake by the phosphorylated sugar reflects the rate of formation of the aldehyde form from the furanose form. 

Transfer of the phosphoryl group to ADP in step 10 then generates ATP and gives enolpyruvate, which undergoes tautomerization to pyruvate. The reaction is catalyzed by pyruvate kinase and requires that a molecule of fructose 1,6-bis-phosphate also be present, as well as 2 equivalents of Mg2+. One Mg2+ ion coordinates to ADP, and the other increases the acidity of a water molecule necessary for protonation of the enolate ion. 

Nucleophilic processes that generate chloroindoles are largely confined to the displacements of oxy functions and Sandmeyer reactions of diazo-nium salts [81 H( 15)547]. A low yield of 2-chloroindole was obtained by a reaction sequence that involved treatment of oxindole with phosphoryl chloride, and then treatment of the Vilsmeier salt with sodium bicarbonate [66JOC2627 86H(24)2879]. It is, however, much better to prepare this compound from 2-lithioindole (92JOC2495). With phosphoryl chloride and dimethylformamide ethyl l-hydroxyindole-2-carboxylate failed to give the expected 3-formyl derivative. Instead there was a 50% yield of the 3-chloro derivative (84CPB3678). Diazonium salts have been used as precursors in... 

Sometimes lateral chlorination can occur on a methyl or alkylthio substituent, especially when phosphorus pentachloride or its mixtures with phosphoryl chloride are used (91JHC1549). Reactions of 2-methyl-4(I//)-quinoline (67) exemplify this behavior (81CPB1069) (Scheme 31) 2-chloro-3- and -4-methyquinolines are also subject to methyl chlorinations by similar reagents (91JHC1549). Sulfuryl chloride and NCS are also likely to induce a proportion of lateral chlorination (83KFZ1055 86S835). 

---