Arylmercurials

Palladation products formed from arylmercurials, carboalkoxymercurials, and alkylmercurials, which have no /3-hydrogen, are used in situ for the reaction of alkenes[367]. Particularly, the arylation of alkenes is synthetically useful. Styrene derivatives 402 and 403 are formed by the reaction of a... 

Alkyl- and arylmercury(II) halides are used for the ketone formation[402]. When active methylene compounds. such as /f-keto esters or malonates are used instead of alcohols, acylated / -keto esters and malonates 546 are produced, For this reaction, dppf is a good ligand[403]. The intramolecular version of the reaction proceeds by trapping the acylpalladium intermediate with eno-late to give five- and six-membered rings smoothly. Formation of 547 by intramolecular trapping with malonate is an example[404]. 

Bisorganomercury compounds with carbonyl groups in the P- and P -positions (10.68) give arylmercury chloride (10.67) together with the dimer (10.69) of the organic residue that is bounded to mercury in the starting material (Hu et al., 1991 yields 10.67 64-98%, 10.69 50-63%). 

The decrease in scientific activity on arylmercury and related arylated metal compounds is probably due to the lack of interest for technological purposes, and to the environmental problems which these compounds cause. 

For transmetallations with a metal (metallo-de-metallations, Scheme 10-95) arylmercury compounds are particularly suitable due to the position of mercury as a noble metal in the electrochemical series of standard potentials (for examples see Makarova, 1970). 

Arylethyl anion 251 Arylferrocenes, from ArN 272 Arylhydrazinedisulfonate 120 Arylmercury compounds 273 ff. Arylpentazoles 123 ff. 

ArSnRs, and with arylmercury compounds. Aryl triflates react with arylbo-ronic acids ArB(OH)2, or with organoboranes, in the presence of a palladium catalyst, to give the arene in what is called Suzuki couplingCyclopropyl groups can be attached to aromatic rings by this reaction. Even hindered boronic acids give good yields of the coupled product. 

Unsymmetrical coupling of vinylic, alkynyl, and arylmercury compounds was achieved in moderate-to-good yields by treatment with alkyl and vinylic dialkylcopper reagents (e.g., PhCH=CHHgCl -t- Mc2CuLi PhCH=CHMe). Unsymmetrical biaryls were prepared by treating a cyanocuprate ArCu(CN)Li (prepared from ArLi and CuCN) with an aryllithium Ar Li. ... 

The conversion of diarylthallium trifluoroacetates to aromatic iodides by treatment with molecular iodine is thus analogous to the well-known conversion of diarylmercury derivatives with iodine to a mixture of an aromatic iodide and an arylmercury iodide (134), but it is much more effective as a synthetic tool because of the spontaneous disproportionation to product of the intermediate arylthallium trifluoroacetate iodide. The present procedure thus provides a practical synthetic method for the ultimate conversion of aryl Grignard reagents to aromatic iodides. 

Under comparable reaction conditions, no C—H bond activation is observed for adducts of 6-Phbipy and 6-Rbipy. Nevertheless, [Au(N,N,C)Cl] derivatives can be obtained with 6-Phbipy [18] and with 6-tBubipy (tBu = CMe3) [20]. The former is obtained by a transmetallation reaction of the arylmercury(II) derivative with [AuClJ, while activation of a C(sp )—H bond of the tert-butyl substituent is accomplished by reaction of the Au(N)Cl3 adduct 3 (N = 6-tBubipy) with AgBp4 in the presence of excess ligand (Scheme 2.2). 

Aromatic compounds react with mercuric salts to give arylmercury compounds.69 Mercuric acetate or mercuric trifluoroacetate are the usual reagents.70 The reaction shows substituent effects that are characteristic of electrophilic aromatic substitution.71 Mercuration is one of the few electrophilic aromatic substitutions in which proton loss from the a complex is rate determining. Mercuration of benzene shows an isotope effect kB/kD = 6,72 which indicates that the [Pg.1026]

The synthetic utility of the mercuration reaction derives from subsequent transformations of the arylmercury compounds. As indicated in Section 7.3.3, these compounds are only weakly nucleophilic, but the carbon-mercury bond is reactive to various electrophiles. They are particularly useful for synthesis of nitroso compounds. The nitroso group can be introduced by reaction with nitrosyl chloride73 or nitrosonium tetrafluoroborate74 as the electrophile. Arylmercury compounds are also useful in certain palladium-catalyzed reactions, as discussed in Section 8.2. 

Aryl derivatives of the heavier group 6 derivatives can also serve for the synthesis of arylmercury compounds.52 For instance, treatment of the diaryltellurium complex 30 with HgCl2 leads to the formation of a coordination complex which undergoes a slow dismutation reaction to afford the arylmercury chloride derivative 31 and the corresponding tellurium species (Scheme 3).53... 

Mercuration reactions provide a convenient approach to a broad range of arylmercury derivatives.82,83 This approach has been applied to a number of substrates, including phenols, indoles, phenylpyridines, and fV-arylamides.83 The products of these reactions as well as their conditions are summarized in Table 1.84 91 Other examples of such reactions include the mercuration of 2-(2 -naphthyl)pyridine (Equation (251)92 and terephthaldehyde (Equation (26))93 with Hg(OCOCF3)2 and Hg(C104)2, which afford 72 and 73, respectively. 

Arylmercury compounds are also often used as starting materials for the synthesis of palladium(ll) complexes. These reactions, whose reagents and products are compiled in Table 3, typically involve the use of chloromercurio derivatives with palladium chloride complexes (entries a-d). 93>95>179-i8i Similar procedures have been applied to the synthesis of ruthenium(ll) and gold(m) complexes (entries e and f).181,182... 

Hydrox5rpyranonate and hydroxypyridinonate complexes have been patented for the treatment of zinc deficiency (451) and are used in zinc supplements. Maltolate and ethylmaltolate complexes of zinc, copper, and tin have been included as essential constituents in patents for formulations for oral care (96). The arylmercury(II) complexes RHgL, where R = 4-XCgH4, X — Me, OMe, NO2, and L — malt, koj, have been tested for antibacterial activity (101). 

Arylmercury chlorides are valuable reagents for the preparation of aryltellurium trichlorides because they are used when the aromatic substrate is not sufficiently reactive for an easy direct condensation with tellurium tetrachloride. ... 

The formed mercury dichloride is separated as a crystalline complex with dioxane. Since the starting arylmercury chlorides are easily prepared from diazonium salts, this method allows the conversion of anilines into aryltellurium trichlorides. 

Diaryltellurium dichlorides (general procedure) TeCl4 (10.8 g, 40 mmol) and arylmercury chloride (80 mmol) are heated under reflux in anhydrous dioxane (100 mL) for 2 h. 

Aromatic compounds react with mercuric salts to give arylmercury compounds.63 The reaction shows substituent effects that are characteristic of electrophilic aromatic... 

Unactivated aryl iodides undergo the conversion Arl — ArCHj when treated with tris(diethylamino)sulfonium difluorotrimethylsilicate and a palladium catalyst.131 A number of methods, all catalyzed by palladium complexes, have been used to prepare unsymmetrical biaryls (see also 3-16). In these methods, aryl bromides or iodides are coupled with aryl Grignard reagents,152 with arylboronic acids ArB(OH)2,153 with aryltin compounds Ar-SnR3,154 and with arylmercury compounds.155 Unsymmetrical binaphthyls were synthesized by photochemically stimulated reaction of naphthyl iodides with naphthoxide ions in an SrnI reaction.156 Grignard reagents also couple with aryl halides without a palladium catalyst, by the benzyne mechanism.157 OS VI, 916 65, 108 66, 67. 

The hydrazone group is hydrolyzed (6-2) during the course of the reaction. Yields are high. Aryl iodides are converted to unsymmetrical diaryl ketones on treatment with arylmercury halides and nickel carbonyl Arl + Ar HgX + Ni(CO)4 —> ArCOAr. 185... 

Aryltin and arylmercury derivatives are converted into fluorobenzene (34) with yields being higher in the case of mercury derivatives.53 56... 

Figure 4.4. Preparation of radioiodinated DOPA from a polystyrene-bound arylmercury precursor [31].

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