Bicyclic phosphates

Synonims 1,2-cyclohexanedicarboxylic, acid calcium salt octacosanoic acid, calcium salt (2 1) calcium difluoride propanedioic acid, calcium salt (1 1) 1,5-pentane dicarboxylic acid, calcium salt (lR,2R,3S,4S)-rel-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, disodium salt mixture of polycarbonic acid salt and inorganic carbonate in a polymeric carrier, sodium 2,2 -methylene-bis-(4,6-di-tert-butylphenyl)phosphate bicyclic (2,2,1) heptane di-carboxylate 1,2-cyclohexanedicarboxylic acid, calcium salt -i- zinc stearate bicyclo[2.2.1]heptane-2,3-dicarbo lic acid, disodium salt, (IR, 2R, 3S, 4S)-rel-and a blend of amorphous silicon dioxide coated wilh 13-docosenamide in a 1 1 ratio proprietary zinc compound octacosanoic acid, calcium salt (2 1) benzoic acid, lithium salt zinc monoglycerolate sodium benzoate encapsulated sodium salts of carbonic and poly-carboxylic acids with styrene and SEES rubber carrier resins zinc,[l,2,3-propanetriolato(2-)-k01,k02]homopolymer, stereoisomer... 

Ozoe et al.76 have determined the Kd values for complexes of ot- and fl-cyclo-dextrin with a variety of 4-substituted bicyclic phosphates (4-substituted 2,6,7-trioxa-l-phosphabicyclo[2.2.2]octane 1-oxides, 1), which are highly toxic convulsants. 

Intermediate 37 can be transformed into ( )-thienamycin [( )-1)] through a sequence of reactions nearly identical to that presented in Scheme 3 (see 22— 1). Thus, exposure of /(-keto ester 37 to tosyl azide and triethylamine results in the facile formation of pure, crystalline diazo keto ester 4 in 65 % yield from 36 (see Scheme 5). Rhodium(n) acetate catalyzed decomposition of 4, followed by intramolecular insertion of the resultant carbene 3 into the proximal N-H bond, affords [3.2.0] bicyclic keto ester 2. Without purification, 2 is converted into enol phosphate 42 and thence into vinyl sulfide 23 (76% yield from 4).18 Finally, catalytic hydrogenation of 23 proceeds smoothly (90%) to afford ( )-thienamycin... 

A further test of the stereoelectronic theory of reactivity of phosphate esters has been attempted using measurements of the rates of displacement of 4-nitrophenate from the esters (23) and (24), their phosphorus epimers, and also (25), in aqueous methanol the introduction of the 4a-Me group into the system would, it was hoped, reduce the the flexibility of the bicyclic structures and so possibly eliminate the participation of twist-boat conformations. The presence of the 4a-Me group has no effect of the rate of displacement of the axial ArO group... 

The A5-phosphorin 164 and the bicyclic compound 165 are precursors of isopropyl metaphosphate, 16). Thermal fragmentation of 165 leads via [2 -I- 2]cycloreversion to triphenyltoluene 166 and isopropyl metaphosphate 167. The latter is identified as isopropyl phosphate after reaction with water. The mass spectrum of 165 is also dominated by this fragmentation picture (m/e 442 (16%) = M + m/e 320 (100%) = M + — 167). 

Langeland and Werstuik <2003CJC525> used ab initio and AIM (atoms-in-molecules) methods to study the structures and reactivity of various phosphate ozonides. Activation energies of the bicyclic complexes (4-ethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane ozonide, l-phospha-2,6,7-trioxabicyclo[2.2.2]octane ozonide, and 1-phos-pha-2,8,9-trioxadamantane ozonide) were found to be significantly higher than the monocyclic structures studied. 

Pavan Kumar et al. <2006NJC717> investigated the reaction of diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD) with cyclic phosphates or phosphoramides in order to determine the structural preferences in spirocyclic penta- and hexacoordinate aminophosphoranes. They found that sulfur would coordinate to phosphorus to form the [3.3.0] bicyclic compounds 94-96. 

The l,2-diacyl-l-/-butylhydrazines have been found to be effective as insect-growth regulators. Caged bicyclic phosphates have also shown promise as insecticides. Wang and Huang have combined these effects in the synthesis of compounds 266 and 267 <2000PS(161)173>. Compounds 268 and 269 have been synthesized for their potential... 

These compounds have been prepared via oxidative addition reactions between the appropriate phosphate or phosphine and either a quinone or via displacement reactions with a suitable diol. Compounds 81 and 83 were prepared by such a displacement reaction between monocyclic pentaoxyphosphorane 317 and 3-fluorocatechol or catechol in toluene, respectively. This reaction takes advantage of the chelation effect of forming a bicyclic system from a monocyclic one <1997IC5730>. Compound 82 and compound 84 were synthesized via oxidation addition between tetrachloroquinone and the respective sulfur-containing cyclic phosphate or phosphine <1997IC5730>. Compound 93 was prepared from the phosphine 318 and the diol 319 in the presence of iV-chlorodiisopropylamine in an ether solution <1998IC93>. 

The equilibrium interconversion between an ethylene phosphite and a bicyclic spirophosphorane is shown to proceed by the insertion of the phosphite into the labile O-H bond of the hydroxyethyl ester. The mechanism is similar to the insertion of carbenes or nitrenes. Energy relationships of reaction intermediates were studied by MO RHF, MP2(full), MP4SDTQ, and DFT calculations. In most cases, they predicted that hydroxyethyl ethylene phosphates were more stable than the strained spirophosphoranes, which is not supported by the experimental evidence. The best correspondence to experimental data was obtained by DFT calculations with Perdew-Wang correlation functions <2003JST35>. 

Monosodium L-glutamate (MSG), 12 49 Monosodium phosphate (MSP), 18 833 manufacture of, 18 853, 857-858 thermal dehydration of, 18 846 Monostatic optical arrangement, 23 139 Monosubstituted boranes, 13 635-636 Monoterpenoid alcohols, 24 500-528 bicyclic, 24 527-528 monocyclic, 24 509-527 Monoterpenoid aldehydes, 24 529-536 Monoterpenoid ethers, 24 528-529 Monoterpenoid hydrocarbons,... 

Propargylic mesylates such as fluorine-substituted derivative 265 react with PhZnCl in the presence of Pd(PPh3)4 (5 mol%) in THF at 0°C within 2 h to provide the anti-Si 2 product in excellent yield and complete transfer of the stereochemistry leading to the allene 266 (Scheme 78). Copper(I) catalyzed allylic substitutions with functionalized diorganozincs proceed with high 8 2 selectivity. Thus, the reaction of the chiral allylic phosphate 267 with 3-carbethoxypropylzinc iodide in the presence of CuCN 2LiCl (2 equivalents) furnishes the awf/-Sjv2 substitution product 268 in 68% yield. By the addition of w-BuLi (1.2 equivalents) and TMSCl (1.5 equivalents), the bicyclic enone 269 is obtained in 75% yield and 93% ee (Scheme 79) . 

A bicyclo[2.2.0]hexan-l-ylmethyl phosphate was reduced by lithium naphthalenide with cleavage of the central bicyclic bond to give a methylenecyclohexane.106... 

Returning to the ATP cleavage reaction, it may be supposed that some metal ions, probably the weakest complexers, form a monocyclic chelate by attaching to the terminal pyrophosphate only (C), whereas others, probably the strongest complexers, form a bicyclic chelate by binding the a-phosphate as well(D). By... 

One example performed in this laboratory is the analysis of toxicity exerted by bicyclic phosphate esters 26). 2,6,7-Trioxa-l-phosphabicyclo[2.2.2]octane-l-oxides (IS) with suitable 4-substituents (R) are highly toxic to mammals 27). The 4-Et derivative... 

Gehrmann and Vogt63) described the polymerization of a bicyclic phosphate 74... 

Two mechanisms (i.e. direct hydrolysis and alternatively a path via an unstable acyl phosphate intermediate) are involved in the hydrolysis in phosphate buffer of N-arylsulfonyl / -lactams such as (130).107 The acyl phosphate intermediate can be trapped with hydrazine. The alkaline hydrolysis of some torsionally distorted lactams, i.e. the bridged benz[rfe]isoquinolin-l-ones (131), in 70% (v/v) DMSO-water has been compared under the same conditions with the hydrolysis of AvA-dimethyl-1 -naphthamide (132). The relative rates of reaction and activation parameters indicate the effect of torsional distortion.108 The reaction of the tricyclic azetidinones (133) with trifluoroacetic acid gives the bicyclic thioesters (135). The mechanism may involve acid-catalysed elimination of methanethiol to give an azetinone intermediate (134) which, after nucleophilic attack of the thiol, is converted into (135).109... 

As seen above with the phosphate receptors, researchers are often not satisfied with only binding their targets, but they also want to mimic enzymes and produce some catalytic activity from their receptors. De Mendoza and collaborators used the bicyclic guanidinium 47 to effect the addition of pyrrolidine to a,p unsaturated lactones [79]. Using a 10% catalyst loading in chloroform, an eightfold reduction in the half-life of the starting materials was observed by... 

The molecular constraint which precludes ligand exchange unambiguously ensures that the tricyclic compounds undergo nucleophilic attack exclusively at the pseudo-equatorial carbon atom, irrespective of the nature of the carbon atom situated in the apical ligand of the TBP. The compounds 1-4 were obtained by alkylation of the chalcogen atom of the corresponding bicyclic (thio)phosphate, 6 and 7, with trialkyloxonium tetrafluoroborate at -78 °c (2). 

Cyclic oligomeric phosphonates with the varying degrees of structural complexity (Structure 5.4) are also available in the market.25 They are widely used as flame-retardant finishes for polyester fabrics. After the phosphonate is applied from an aqueous solution, the fabric is heated to swell and soften the fibers, thus allowing the phosphonate to be absorbed and strongly held. It is also a useful retardant in polyester resins, polyurethanes, polycarbonates, polyamide-6, and in textile back coatings. A bicyclic pentaerythritol phosphate has been more recently introduced into the market for use in thermosets as well as for polyolefins (preferably, in combination with melamine or ammonium polyphosphate)... 

There have been relatively few reports concerning the chemistry of fused 5-6 bicyclic systems with one heteroatom in the five-membered ring and three in the six-membered ring, so this is a field of chemistry which is very open to new research. The only classes of compounds which have been widely reported are the S -nucleoside cyclic phosphates (1) and their analogues. Many thousands of papers have been written concerning these molecules in contrast to the very small number... 

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