Thallium acetate alkenes

Thallium acetate reacts with iodine and an alkene to give the trans-io do acetate derivatives in 90% yield (28) ... 

Thallium(III) acetate reacts with alkenes to give 1,2-diol derivatives (see p. 128) while thallium(III) nitrate leads mostly to rearranged carbonyl compounds via organothallium compounds (E.C. Taylor, 1970, 1976 R.J. Ouelette, 1973 W. Rotermund, 1975 R. Criegee, 1979). Very useful reactions in complex syntheses have been those with olefins and ketones (see p. 136) containing conjugated aromatic substituents, e.g. porphyrins (G. W. Kenner, 1973 K.M. Smith, 1975). 

Alkenes can also be oxidized with metallic acetates such as lead tetraacetate or thallium(III) acetate " to give bis-acetates of glycols. Oxidizing agents such as benzoquinone, Mn02, or 02, along with palladium acetate, have been used to convert conjugated dienes to l,4-diacetoxy-2-alkenes (1,4 addition). ... 

Primary (R = H) and secondary aromatic amines react with alkenes in the presence of thallium(III) acetate to give vie- diamines in good yields. " The reaction is not successful for primary aliphatic amines. In another procedure, alkenes can be diaminated by treatment with the osmium compounds R2NOSO2 and R3NOSO (R = t-Bu)," analogous to the osmium compound mentioned at 15-51. The palladium-promoted method of 15-51 has also been extended to diamination. " Alkenes can also be diaminated indirectly by treatment of the aminomercurial compound mentioned in 15-51 with a primary or secondary aromatic amine. 

A somewhat similar catalytic acetoxylation of ethylene to vinyl acetate by 02 has been carried out in acetic acid in the presence of a Pd(OAc)2-pyCo(TPP)N02 system.472 A stoichiometric epoxidation of alkenes such as 1-octene or propene by cobalt-nitro complexes has been shown to occur in the presence of thallium(III) benzoate. Oxygen labeling studies showed that the epoxide oxygen atom comes only from the nitro ligand (equation 197).473... 

Since silver salts are expensive, other cheaper reagents have been sought which can bring about the same type of conversion, and the iodine- tassium iodate- tassium acetate combination has been found to provide a useful alternative. Thallium(I) acetate may be used in place of silver acetate in the Woodward procedure, and syn hydroxylation of steroidal alkenes with dialliumflll) acetate in acetic acid has been performed. ... 

The reaction of alkenes with thallium(III) acetate (TTA) forms oxythallium adducts (52) in a similar manner to the case of oxymercuration. The thallium moiety of adducts can be replac by a halogen atom by heating with coppeKI) salts (CuX-KX X = I, Br, Cl) in acetonitrile (equation 24). ° ... 

Thallium monoacetate, TIOCOCH3 (hygroscopic), behaves similarly to silver acetate or silver benzoate. In the presence of iodine, it accomplishes stereoselective hydroxylations of alkenes [410]. 

Acyl esters of vicinal diols are obtained by the reaction of alkenes with metal carboxylates [436]. Lead tetraacetate in acetic acid at 70 °C converts 1,2-dihydronaphthalene to rranj-l,2-diacetoxy-l,2,3,4-tetrahy-dronaphthalene in 72% yield [436]. The reaction is not always stereospecific. Cyclohexene treated with thallium triacetate gives a mixture of diastereomers in varying ratios, depending on reaction conditions, and byproducts as a result of rearrangements (equation 89) [411],... 

Pans-2-Iodocyclohexyl acetate can be isolated in essentially quantitative yield from the reaction of thallium(I) acetate, iodine, and cyclohexene in a 1 1 1 molar ratio in refluxing chloroform. lodo acetates from a representative series of alkenes including cyclohexene have been similarly prepared in 80-98% yield in glacial acetic acid which was not dried as described in this procedure. The corresponding iodo benzoates are obtained in comparable yields from reaction with thallium(I) benzoate and iodine in benzene. The deactivated olefin methyl cinnamate did not react under these conditions, and o-allylphenol underwent ring iodination to... 

Alkenes and alcohols condense with nitriles under drastic acidic conditions. In most cases sulfuric acid is used either neat or with solvents such as acetic acid. In liquid hydrogen fluoride containing defined amounts of water, nitriles react with linear or branched alkenes to form amides in good yields. Treatment of allylsilanes and allylstannanes with thallium(III) salts in acetonitrile activates Ae alkene for nucleophilic attack of the nitrile group. The generated nitrilium cation (equation 23) is hydrolyzed to the corresponding )V-allylamide. ... 

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