Thallium tosylate

Oxidation of easily enoUzable ketones such as alkyl aryl ketones affords either a-oxylated ketones or carboxyhc acid derivatives via oxythallation of the enol forms, the products depending on the kind of Tl(lll) salts and/or solvents employed (Scheme 9.24). Use of TTN usually induces aryl group migration leading to the formation of carboxyhc acids or their esters [26], making this oxidative transformation useful for organic synthesis (Schemes 9.25 [27], 9.26 [28], 9.27 [29] and 9.28 [30]). Use of TTA, thallium tosylate [ l l(OTs), ], thallium triflate [ l1(()Tf), ], and thallium mesylate [ l1(()Ms)j, on the other hand, produces -oxylated ketones which sometimes further react to give useful compounds (Schemes 9.29 [31], 9.30 [32], 9.31 [33], 9.32 [34] and 9.33 [35]). 

N-Alkylations, especially of oxo-di- and tetra-hydro derivatives, e.g. (28)->(29), have been carried out readily using a variety of reagents such as (usual) alkyl halide/alkali, alkyl sulfate/alkali, alkyl halide, tosylate or sulfate/NaH, trialkyloxonium fluoroborate and other Meerwein-type reagents, alcohols/DCCI, diazoalkanes, alkyl carbonates, oxalates or malon-ates, oxosulfonium ylides, DMF dimethyl acetal, and triethyl orthoformate/AcjO. Also used have been alkyl halide/lithium diisopropylamide and in one case benzyl chloride on the thallium derivative. In neutral conditions 8-alkylation is observed and preparation of some 8-nucleosides has also been reported (78JOC828, 77JOC997, 72JOC3975, 72JOC3980). 

The use of alkyl tosylates generally leads to predominant TV-alkylation (e.g. 76JOC875), as does the alkylation of the thallium salts of pyrrole or indole (70JCS(C)2563,71JOC3993,81S389). 

NMO NMP Nu PPA PCC PDC phen Phth PPE PPTS Red-Al SEM Sia2BH TAS TBAF TBDMS TBDMS-C1 TBHP TCE TCNE TES Tf TFA TFAA THF THP TIPBS-C1 TIPS-C1 TMEDA TMS TMS-C1 TMS-CN Tol TosMIC TPP Tr Ts TTFA TTN N-methylmorpholine N-oxide jV-methyl-2-pyrrolidone nucleophile polyphosphoric acid pyridinium chlorochromate pyridinium dichromate 1,10-phenanthroline phthaloyl polyphosphate ester pyridinium p-toluenesulfonate sodium bis(methoxyethoxy)aluminum dihydride (3-trimethylsilylethoxy methyl disiamylborane tris(diethylamino)sulfonium tetra-n-butylammonium fluoride f-butyldimethylsilyl f-butyldimethylsilyl chloride f-butyl hydroperoxide 2,2,2-trichloroethanol tetracyanoethylene triethylsilyl triflyl (trifluoromethanesulfonyl) trifluoroacetic acid trifluoroacetic anhydride tetrahydrofuran tetrahydropyranyl 2,4,6-triisopropylbenzenesulfonyl chloride 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane tetramethylethylenediamine [ 1,2-bis(dimethylamino)ethane] trimethylsilyl trimethylsilyl chloride trimethylsilyl cyanide tolyl tosylmethyl isocyanide meso-tetraphenylporphyrin trityl (triphenylmethyl) tosyl (p-toluenesulfonyl) thallium trifluoroacetate thallium(III) nitrate... 

The carboxylic acid 61 was converted to its aldehyde counterpart which, upon condensation with m-terf-butyldimethylsilyloxyphenyl-magnesium bromide, gave the alcohol 62. Conversion of the alcohol to the acetamide 63 was effected by a one-pot tosylation/sodium azide displacement, followed by hydrogenation (H2/Pd(C)/Florisil) and acetylation. Treatment of 63 by thallium(III) trifluoroacetate (TTFA)... 

Reactions of Indoles. 2-Arylindoles react with tosyl azide under phase-transfer conditions to give 3-diazo-compounds (148). The phenylazoindole (149 R = N2Ph) is converted into the nitroindole (149 R = NO2) by ipso-nitration. Indoles are oxidized by thallium(III) nitrate to mixtures of oxindoles and isatins. Sensitized photo-oxygenation of the indole (150) yields the hydroperoxide (151), which forms compound (152) on treatment with methanolic potassium borohydride. Vilsmeier-Haack formylation of... 

PCC PDC Pent Ph pyridinium chlorochromate pyridinium dichromate n-pentyl phenyl TBHP TPP Tr Ts TTN f-butyl hydroperoxide tetraphenylporphyrin trityl (triphenylmethyl) tosyl (p-toluenesulfonyl) thallium(III) nitrate... 

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