Silver-catalyzed oxidative decarboxylation

The nucleophilic radicals formed by the silver-catalyzed, oxidative decarboxylation of carboxylic acids by peroxydisulfate ions attack protonated imidazoles mainly at the 2-... 

Imidazoles normally undergo free-radical reactions at the 2-position. For example, homolytic free-radical alkylation of histidines and histamines yields 2,3-disubstituted histidines and histamines. In these reactions, the free radical was generated via silver-catalyzed oxidative decarboxylation of acids with peroxydisulfate 433 (Scheme 103) <2001BML1133>. 

Radical substitution reactions include alkylations and arylations in the main. Nucleophilic radicals produced by the silver-catalyzed oxidative decarboxylation of carboxylic acids (by peroxydisulfate ion) attack proton-ated azoles at the most electron-deficient sites.Thus, imidazole and 1-alkylimidazoles are methylated exclusively at C-2 in rather low yields. The use of isopropyl and t-butyl radicals gives improved yields, but benzyl and acyl radicals tend to dimerize rather than substitute the... 

Silver(I) catalyzed oxidative decarboxylation using peroxydisulfate is well studied . Decarboxylated carbon radicals can form a C—C bond with 1,4-benzoquinone or 1,4-naphthoquinone (equation 17) . In the case of 1,4-benzoquinone and phenylacetic acid the yield is 87%, whereas in the case of 2-methyl-l,4-naphthoquinone and cyclopropanecar-boxylic acid the yield is as low as 37%. 

The regioselective C3-alkenylation of thiophene-2-carboxylic acids was achieved via rhodium/silver-catalyzed oxidative coupling, accompanied by decarboxylation (13JOC7216). The catalyst can also be used for ort/zo-alkenylation of benzoic acids. 

Alkyl radicals for such reactions are available from many sources such as acyl peroxides, alkyl hydroperoxides, particularly by the oxidative decarboxylation of carboxylic acids using peroxy-disulfate catalyzed by silver. Pyridine and various substituted pyridines have been alkylated in the 2-position in high yield by these methods. Quinoline similarly reacts in the 2-, isoquinoline in the 1-, and acridine in the 9-position. Pyrazine and quinoxaline also give high yields of 2-substituted alkyl derivatives <74AHC(16)123). 

Myers oxidative decarboxylative Heck reaction became the prototype for a whole series of regiospecific oxidative couplings in which carboxylic acids adopt the reactivity of aryl electrophiles in the corresponding redox-neutral processes [67-72]. Crabtree et al. developed a process in which arenes react with aromatic carboxylates under C-H activation in the presence of a palladium catalyst and excess silver carbonate to yield biaryls. This reaction is useful especially for intramolecular couplings (Scheme 20) [73, 74]. Recently, a palladium-free, silver-catalyzed radical variant has been disclosed [78]. 

Generation of tert-Butyl Radicals via Oxidative Decarboxylation. Silver-catalyzed decarboxylation of carboxylic acids by persulfate generates alkyl radicals, which have been used for ho-molytic alkylation of aromatic bases. Pivalic acid is a source of f-butyl radicals in this process. 2-f-Butylquinoline is formed re-gioselectively by this method (eq 3) 6-r-butylnicotine has been prepared in a similar way. ... 

The silver(II)-catalyzed decarboxylation of carboxylic acids was noted in Section 54.2.2.2. The oxidation of amino acids is thought to occur by a similar process. 

Oxalic and malonic acids, as well as a-hydroxy acids, easily react with cerium(IV) salts (Sheldon and Kochi, 1968). Simple alkanoic acids are much more resistant to attack by cerium(IV) salts. However, silver(I) salts catalyze the thermal decarboxylation of alkanoic acids by ammonium hexanitratocerate(IV) (Nagori et al., 1981). Cerium(IV) carboxylates can be decomposed by either a thermal or a photochemical reaction (Sheldon and Kochi, 1968). Alkyl radicals are released by the decarboxylation reaction, which yields alkanes, alkenes, esters and carbon dioxide. The oxidation of substituted benzilic acids by cerium(IV) salts affords the corresponding benzilic acids in quantitative yield (scheme 19) (Hanna and Sarac, 1977). Trahanovsky and coworkers reported that phenylacetic acid is decarboxylated by reaction with ammonium hexanitratocerate(IV) in aqueous acetonitrile containing nitric acid (Trahanovsky et al., 1974). The reaction products are benzyl alcohol, benzaldehyde, benzyl nitrate and carbon dioxide. The reaction is also applicable to substituted phenylacetic acids. The decarboxylation is a one-electron process and radicals are formed as intermediates. The rate-determining step is the decomposition of the phenylacetic acid/cerium(IV) complex into a benzyl radical and carbon dioxide. 

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