Arylmercury compounds

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. ... 

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... 

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... 

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. 

Arylpalladium salts ArPdX prepared from arylmercury compounds and lithium palladium chloride couple with allylic chlorides in moderate yields,... 

The sensitivity of plants to mercury compounds are different. In general, the fungitoxic concentration does not harm the seeds and bulbs of the plants the therapeutic index of mercury compounds for seed treatment is therefore satisfactory. Potato seed is an exception because it is susceptible to many species. However, only aryl mercury compounds are suitable for foliage application, and these only in the case of certain plants or in certain stages of development. Thus, phenylmercury acetate or chloride are not phytotoxic to apple trees in the prebloom period. Arylmercury compounds are not phytotoxic to the rice plant at all. Phytotoxicity is mainly caused primarily by mercury vapours formed on the reduction of mercury compounds (Hitchcock and Zimmermann, 1957). According to Lee et at. (1973), mercury compounds inhibit the biochemical reactions of the electron transport of photosynthesis, depending on the pH value and on the concentration. 

MeHg" " is distributed throughout the body, and easily penetrates the blood-brain and blood-placental barriers (Clarkson 1993, Hansen et al. 1989, Suzuki et al. 1984). The transport of MeHg" " into tissues is mediated by the formation of a MeHg-cysteine complex (Aschner and Aschner 1990, Tanaka et al. 1991, Kerper et al. 1992). Soon after application, McHg" " is found in the blood, predominantly in the red cells. In humans, the ratio of MeHg in red blood cells to serum is approximately 20 1 (Kershaw et al. 1980). Short-chain alkyl-mercury compounds such as methylmercury or ethylmercury are rather stable in the body, whereas long-chain alkylmercury or arylmercury compounds such as phenylmercury may be metabolized relatively quickly to Hg " " ions (Roberts et al. 1979) and, therefore, show similar behavior to the Hg " " ion (Pfab et al. 

Organomercurials - particularly the alkyl- and arylmercury compounds - are more active as bactericides or fungicides than the inorganic salts. Phenylmercury acetate prevents the growth of a variety of fungi in vitro at concentrations of approximately 0.125 mg L whereas ethylmercury salts are active at 0.05 mg In contrast, mercuric acetate or chloride are active at 1.0 mg L . The difference may partly be attributed to lipid solubility, where penetra-... 

This reaction is applied to a wide range of alkenes such as acrylic esters, styrene, ethylene, 1-alkene, 1,3-dienes, allyl chloride, allyl acetate, and vinyl ethers [122]. Tolerance of the arylmercury compounds to polar functional groups in the substrate renders the reaction applicable to the synthesis of many functionalized styrene derivatives. A ferrocenyl mercury compound undergoes addition to alkene via the Heck type reaction of methyl methacrylate (Eq. 5.29) [123]. 

In recent years, some interesting reactions that involve metal-exchange reactions of arylmercury compounds with Pd(II) salts have been developed. The resulting organopalladium species serve as a source of reactive intermediates that lead to products. Some of the types of compounds that can be formed via the unstable palladium intermediates are illustrated below ... 

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