Bases Cesium carbonate

Decomposition with Bases. Alkaline decomposition of poUucite can be carried out by roasting poUucite with either a calcium carbonate—calcium chloride mix at 800—900°C or a sodium carbonate—sodium chloride mix at 600—800°C foUowed by a water leach of the roasted mass, to give an impure cesium chloride solution that is separated from the gangue by filtration (22). The solution can then be converted to cesium alum [7784-17-OJ, CS2SO4 Al2(S0 2 24H20. Extraction of cesium from the poUucite is almost complete. Solvent extraction of cesium carbonate from the cesium chloride solution using a phenol in kerosene has also been developed (23). 

The most demanding test of cesium carbonate as base was with 2,3-dihydroxypyridine (3-hydroxypyridone). The cesium salt was found to be fairly unstable, apparently oxidizing quite rapidly. Model reactions suggested that alkylation would occur 1,3 (N, 0) to give the substituted pyridone. Nevertheless, on the basis of UV and H-nmr analysis, the product of reaction between 2,3-dihydroxypyridine and tetraethylene glycol dibromide was assigned as the pyridocrown (23% yield, mp 77—78.5°) as shown in Eq. (3.60). 

For the installation of the pyrrolidinylethanol moiety 10 on the aryl group, we first tested Buchwald s Cu-catalyzed conditions with 10, aryl iodide 12, Cs2C03, Cul and 1,10-phenanthroline at 110°C in toluene to prepare the penultimate 49 [14a], The reaction was very slow, giving only 5-10% conversion even after 2 days. The reaction was faster at higher temperatures but two impurities 50 and 51 were observed (Scheme 5.14). To find the optimal conditions, xylene and diglyme were tested as solvents, lithium, potassium and cesium carbonates were screened as bases and 2,2 -bipyridy], TMEDA and l-(2-dimethylaminoethyl)-4-methylpiperazine were examined as ligands. The optimized protocol was identified as 10mol% of... 

With the nitro group successfully introduced, the aromatic fluoride substituent in 11 was ready to undergo the nucleophilic aromatic substitution with the hydrox-ypyridine 9. The reaction proceeded smoothly in DMF at 55 °C using an equimolar amount of cesium carbonate as the base and provided a 90% isolated yield of 23 after crystallization. With compound 23 in hand, only the reduction of the nitro... 

Another example where PEG played the role of polymeric support, solvent, and PTC was presented by the group of Lamaty [72]. In this study, a Schiff base-proteded glycine was reacted with various electrophiles (RX) under microwave irradiation. No additional solvent was necessary to perform these reactions and the best results were obtained using cesium carbonate as an inorganic base (Scheme 7.64). After alkylation, the corresponding aminoesters were released from the polymer support by transesterification employing methanol in the presence of triethylamine. 

In terms of A -substitution, Hartwig reported improved conditions for the Pd(0) catalyzed N-arylation of indoles and pyrrole <99JOC5575>. It was found that when commercially available P(<-Bu)3 was employed as ligand and cesium carbonate as base, the reaction between indoles 95 and unhindered aryl bromides 96 or chlorides occurred under milder conditions than the Pd(OAc)2/DPPF system previously reported yielding the A/-arylated products 97. Alternatively, it has been found that pyrrole- and indole-2-carboxylic acid esters can be selectively 7V-arylated with phenylboronic acids in the presence of cupric acetate and either tiiethylamine or pyridine <99T12757>. 

The etherification of support-bound phenols with alkyl halides is usually performed in dipolar aprotic solvents (DMF, NMP, DMSO) in the presence of bases such as DBU, KN(SiMe3)2, phosphazenes [149], or cesium carbonate (Entries 6 and 7, Table 7.11). 

Non-activated aryl bromides (but not fluorides) can be used as substrates for palla-dium(0)-catalyzed aromatic nucleophilic substitutions with aliphatic or aromatic amines. These reactions require sodium alcoholates or cesium carbonate as a base, and sterically demanding phosphines as ligands. Moreover, high reaction temperatures are often necessary to achieve complete conversion (Entries 7 and 8, Table 10.4 Experimental Procedure 10.1). Unfortunately, the choice of substituents on the amine... 

Diastereoselective Mannich-type reactions between ketene silyl acetals and chiral sulfinimines using simple metal-free Lewis bases such as tetraalkylammonium car-boxylates have been reported. The sulfinimine can even be generated in situ (from aldehyde and a chiral sulfonamide), using cesium carbonate, followed by addition of ketene silyl acetal at -78 °C, and as little as 1 mol% of catalyst.32... 

Heck and Suzuki type couplings have been described by Fu [2] et al. The reaction of chlorobenzene and styrene in refluxing dioxane in the presence of [Pd2(dba)3 ] and the electron rich tri-tert.-butyl-phosphane [eq. (a)] gives rise to trans-stilbene in 83% yield. Besides the choice of the ligand - aryl phosphanes, tri-n-butyl-phosphane or tri-cyclo-hexyl-phosphane show no conversion - the base is also crucial for success. Cesium carbonate gives the best results, although the cheaper potassium phosphate gives comparable yields. 

The group of Harmata has explored a route that can be used to effectively couple aryl chlorides with methylphenylsulfoximines [100]. Using palladium acetate and rac-binap with a large excess of aryl chlorides as coupling partners and cesium carbonate as the base, yields of 10-94% were attained after one or two 1.5-hour irradiation periods at 135 °C. Switching to an aryl tri-flate, and using a surplus of the sulfoximines (five equivalents) furnished an impressive 94% yield (Scheme 32). 

For the C-C bond-forming step coordination of an electrophilic aryl palladium halide to a cyclopentadienyl anion is assumed, followed by reductive elimination. Presumably the Pd catalyst is not involved in the C-H bond-breaking step, which is interpreted as an apparently simple deprotonation with cesium carbonate as base. The overall process is similar to the arylation of other soft nucleophiles [9]. 

Imidazole-containing compounds have been utilized as reagents for various synthetic transformations. A convenient access to substituted allyl enol carbonates was established through the reaction of ketone enolates with the complex of allyl l//-imidazole-l-carboxylates 74 and boron trifluoride etherate <07JOC9372>. Relatively mild and highly efficient Cul-catalyzed /V-arylation procedures for imidazoles with aryl and heteroaryl bromides or chlorides have been developed in the presence of ligands 75 and cesium carbonate <07JOC2737>. a, -Unsaturated 2-acyl imidazoles 76 are an alternative and practical class of dienophiles for the DNA-based catalytic asymmetric Diels-Alder reaction in... 

The reduction of the di(selenocyanato)propane 169 with sodium borohydride gave the corresponding diselenolate, which reacted with 3-chloropropan-l-thiol to give the dithiol 238 in 60% yield. A soft base like cesium carbonate in DMF was able to deprotonate the dithiol and treatment with 1,3-dibromopropane afforded the sulfur and selenium 16-membered ring heterocycles 239 in 22% yield <2000IC2558>. Bis(o-formylphenyl)telluride 241 was synthesized... 

Allyl bromide, methyl iodide and benzyl bromide are the triumvirate of common alkyl halides that alkylate metal alkoxides readily. In the case of phenols, potassium carbonate [Scheme 4.230]438 or cesium carbonate are competent bases whereas primary and secondary alcohols require potassium hydroxide [Scheme 4.231J,402 but the strongly basic conditions limit the scope of the method. For example, attempts to alkylate the secondary and phenolic hydroxyl groups of the intermediate 232.1 in a synthesis of the antibiotic Nogalamycin using the traditional metal alkoxide alkylation failed owing to competing sec-... 

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