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Palladium(II)-catalyzed oxidative coupling of arenes by thallium(III)

1983; Elsevier BV; Volume: 39; Issue: 14 Linguagem: Inglês

10.1016/s0040-4020(01)91964-7

1464-5416

Anatoly K. Yatsimirsky, Sergei A. Deiko, Alexander D. Ryabov,

Oxidative Organic Chemistry Reactions

Oxidation of benzenes with electron-donating and moderate electron-withdrawing substituents by thallium(III) trifluoroacetate in the presence of catalytic amounts of palladium(II) acetate affords biaryls in good yields. The GLC study of the isomer distribution has shown that 4,4 '-biaryls are the major products. Thus, the pure 4,4 '-biaryls can be easily isolated either by recrystallization or column chromatography. The competitive experiments and kinetic study using arenes and arylthallium derivatives as starting materials as well as quenching experiments have demonstrated the first step of the reaction to be fast thallation of arene to form arylthallium intermediate ArTl (OOCCF3)2. The latter undergoes the rate-determining transmetallation step reacting with monomeric complex Pd(OAc)2, which is formed upon depolymerization of trimer Pd3(OAc)6. Subsequent fast decomposition of arylpalladium species gives the final reaction products. The thallation of arene and substitution of TlIII for PdII in ArTl (OOCCF3)2 are characterized by the slopes of Hammett plots of -5.6 (XXX+) and -3.0 (XXX), respectively.