Arenes thallation

Lead(IV) trifluoroacetate in TFAH is a very reactive electrophile that is capable of plumbylating less electron-rich arenes. Nonetheless, the use of trifluoroacetate anions in the plumbylation reactions should be avoided, because aryllead(IV) tri-fluoroacetates are unstable compounds that readily decompose to the corresponding aryl trifluoroacetates and biaryls [34—37, 40, 41]. It has been reported [41] that 4-FC6H4ArPb(TFA)3 is reasonably stable and can be isolated from the reaction of Pb(TFA)4/TFAH with fluorobenzene. A mechanistic study [41] indicated an electrophilic substitution path for the plumbylation reaction, which seemed to be substantially more para-selective than mercuration and thallation. For example, the plumbylation of toluene with Pb(OAc)4 in dichloroacetic acid has been reported [41] to occur with >90 % para-selectivity. 

The carboxylates of indium and thallium are obtained by dissolving the oxides in acid. Acetate and trifluoroacetate salts are used extensively as reagents in organic synthesis. Certain other thallium compounds have been used also. The trifluoroacetate, T1(02CCF3)3, will directly thallate aromatic compounds to give arylthal-lium species, for example, C6H5T1(02CCF3)2 (cf. aromatic mercuration, Section 15-15) and oxidize arenes to biaryls. 

Aryl nitriles. Arylthallium bis(trifluoroacctatcs) react with CuCN in refluxing CH,CN to give aryl nitriles in 60-85% yield, A one-pot synthesis is possible by thallation of the arene in CH,CN. 

Biaryls. Biaryls can be prepared by oxidative coupling of arenes with palladium(II) compounds, but the coupling is not regioselective. Regioselectivity is considerably improved by use of TTFA as oxidant and only catalytic amounts of Pd(OAc),. Formation of 4,4 -biaryls is favored from arenes substituted with either electron-donating or moderately electron-withdrawing substituents. The first step is thallation to form ArTlfOCOCF,)-. Example ... 

Figure 6 Direct relationship of the relative reactivities (Jt i) of arenes in mercuration and thallation...

The linear free enogy relationship obsoved for arene donors relates the activation barrier AG for aromatic substitution directly to the CT transiticxi oiergy Aver of the EDA complex. Since Aver pertains to the energetics of the photoionizadons in equations (27) and (28), the correlation suggests that these arene contact ion pairs ate reasonable approximatims to the transition states for both mercuration and thallation, e.g. Scheme 6. 

Indeed the diversion to side products during thallation coincides with the direct obsovation of the arene radical cation as a transient intermediate both by UV-visible and ESR spectroscopy. A similar dichotomy between the products of mercuration and thallation exists with durene, albeit to a lesser degree. Finally no discrepancy is observed with mesitylene, nuclear substitution occuiring exclusively in both mercuration and thallation. Such a divergence between mercuration and thallation can be reconciled by the formulation in Scheme 6 if they difier by the extent to which di sive separation (ki) occurs in equation (31). All factors being the same, diffusive separation of the radical pair from thallium(III) should... 

The study of mercuration and thallation provides a shaip focus on the experimental delineation of stepwise and concerted mechanisms for arene activation. Thus the unequivoc demonstration of arene radical cations as key intermediates in thallation, particularly of durene and pentamethylbenzene, is consistent with a stepwise (electron-transfer) mechanism for arene activation (compare Scheme 6 and equation 39). 

Accordingly, a reaction mechanism has been proposed [113] which includes one-electron transfer from the arene donor to the high-valent metal within the EDA complex as the critical first step toward mercuration or thallation, (Eq. 27) ... 

The formation of iodobenzene by treatment of phenylthallium(III) compounds with potassium iodide was reported, without experimental details, by Challenger et al in the 1930 s. 2,113 jhe potential and synthetic interest of this iododethallation reaction was extensively studied by McKillop and Taylor in the early 1970 s.8 7-89 Although arylthallium(III) compounds prepared by reaction of the arenes with thallium tris(trifluoroacetate) (84) can be isolated, they can also be directly converted into aryl iodides by addition of aqueous potassium iodide to the thallation reaction mixture. An intermediate arylthallium(III) diiodide (91) was suggested to be formed and to decompose intramolecularly to lead to the aryl iodide. ... 

Thallium(III) trifluoroacetate is prepared in >90% yield by heating a suspension of Tl(III) oxide in trifluoroacetic acid. This mixture can be used directly for thallation. Oxidative coupling of electron-rich arenes may be avoided by using 1 1 Tl(III) trifluoroacetate and ether in trifluoroacetic acid . For acid-sensitive substrates, it is preferable first to isolate the solid Tl(III) trifluoroacetate by evaporation of the acid. This can then be used in CHjCN as the thallating agent. ... 

One important mechanism for homogeneous catalytic activation of aromatic C—H bonds is electrophilic attack by transition-metal complexes on the aromatic substrates. It is presumed t -aryl complexes are important intermediates in these reactions, but they are rarely isolated. Direct electrophilic metallation of aromatic substrates is closely related to reactions observed with nontransition metals ( 5.6., auration 5.7.2., mercuration and 5.3., thallation - ). References to metal-aryl complexes synthesized by electrophilic attack on arenes by transition metals are sununarized in Table 1. Reviews are available " . 

---