Organomercurial

The Pd-mediated coupling involving organomercury and alkenes is useful for the synthesis of C-5 substituted 2 -deoxyribonucleosides[376]. The ethylur-idine 415 is prepared by the reaction of the 5-chloromercuriuridine 414 with... 

Addition of several organomercury compounds (methyl, aryl, and benzyl) to conjugated dienes in the presence of Pd(II) salts generates the ir-allylpalladium complex 422, which is subjected to further transformations. A secondary amine reacts to give the tertiary allylic amine 423 in a modest yield along with diene 424 and reduced product 425[382,383]. Even the unconjugated diene 426 is converted into the 7r-allyllic palladium complex 427 by the reaction of PhHgCI via the elimination and reverse readdition of H—Pd—Cl[383]. 

Pd(II) salts promote the carbonylation of organomercury compounds. Reaction of phenylmercury chloride and PdCh under CO pressure affords benzophenone (429)[387]. Both esters and ketones are obtained by the carbonylation of furylmercury(Il) chloride in alcohol[388]. Although the yields are not satisfactory, esters are obtained by the carbonylation of aryl- and alkylmercuryfll) chlorides[389,390]. One-pot catalytic carbonylation of thiophene, furan, and pyrrole (430) takes place at the 2-position via mercuration and transmetallation by the use of PdCb, Hg(N03), and CuCl2[391]. 

Mercuration. Mercury(II) salts react with alkyl-, alkenyl-, and arylboranes to yield organomercurials, which are usehil synthetic intermediates (263). For example, dialkyhnercury and alkyhnercury acetates can be prepared from primary trialkylboranes by treatment with mercury(II) chloride in the presence of sodium hydroxide or with mercury(II) acetate in tetrahydrofuran (3,264). Mercuration of 3 -alkylboranes is sluggish and requires prolonged heating. Alkenyl groups are transferred from boron to mercury with retention of configuration (243,265). 

When an aqueous effluent stream containing organomercurials cannot be recycled, it may be treated with chlorine to convert the organomercury to inorganic mercury. The inorganic compounds thus formed are reduced to metallic mercury with sodium borohydride. The mercury metal is drained from the reactor, and the aqueous solution discarded. The process utilising sodium borohydride is known as the Ventron process (27). 

With mercuric acetate (Hg(OOCCH2)2), olefins and / fZ-butyl hydroperoxide form organomercury-containing peroxides (66,100). The organomercury compound can be treated with bromine or a mild reducing agent, such as sodium borohydride, to remove the mercury. 

Halophosphines can be treated with organometaUic reagents, eg, Grignard reagents, organomercuries, and organolithiums, to produce tertiary phosphines. 

The reactivity of mercury salts is a fimction of both the solvent and the counterion in the mercury salt. Mercuric chloride, for example, is unreactive, and mercuric acetate is usually used. When higher reactivity is required, salts of electronegatively substituted carboxylic acids such as mercuric trifiuoroacetate can be used. Mercuric nitrate and mercuric perchlorate are also highly reactive. Soft anions reduce the reactivity of the Hg " son by coordination, which reduces the electrophilicity of the cation. The harder oxygen anions leave the mercuric ion in a more reactive state. Organomercury compounds have a number of valuable synthetic applications, and these will be discussed in Chapter 8 of Part B. 

Another major route to fluorinated organomercury compounds is thermal or photochemical decarboxylation offluonne-conlaining mercury carboxylates [/-Si, 169, 170,171, 172], as shown for example in equation 125 [153, 169] Via similar methodology, C6HjHgCF3 (60-75%) [171], (CF3)2Hg (92%) [/i59T, (02NCFCl)2Hg (58%) [172], and [(CF3)3C]2Hg (80%) [157] were synthesized, and several of these mercurials have been used as fluorocarbene precursors [166],... 

Larock, R C Organomercury Compounds in Organic Synthesis Springer-Verlag Berlin, 1985 Seyferth D Acc Chem Res 1972, 5 65... 

The reaction between an excess of Li and an organomercury compound is a useful alternative when isolation of the product is required, rather than its direct use in further synthetic work ... 

These reactions work best with X = I but the less-expensive RBr can be used in conjunction with a Zn-Cu alloy instead of pure Zn. Diaryls are best obtained from appropriate organoboranes or organomercury compounds ... 

An enormous number of organomercury compounds are known. They are predominantly of the same stoichiometries as those of Zn and Cd, viz. RHgX and HgR2, and may be prepared by the action of sodium amalgam on RX ... 

Interaction of the thiophene-containing organomercury compounds 272 (R = H, Me, Et) [74MI1, 79JCS(D)2037] with potassium tris(3-methylpyrazolyl) borate (KTp ) yields 273 [96JOM(515)213],... 

Cacchi and Palmier (83T3373) investigated a new entry into the quinoline skeleton by palladium-catalyzed Michael-type reactions. They found that phenyl mercurial 134 was a useful intermediate for the synthesis of quinoline derivatives, and that by selecting the reaction conditions the oxidation level of the heterocyclic ring in the quinoline skeleton can be varied. On such example is shown in Scheme 16. PdCla-catalyzed coupling between organomercurial reagent 134 and enone 135 delivered adduct 136 which was subsequently cyclized to quinoline 137 under acidic conditions. 

Abstraction of H+ from the protonated enol by water gives an organomercury compound. 

Organomercury compounds, reaction with NaBH4, 222 Organometallic compound, 345 polarity of, 143... 

Reviews of the use of organomercury compounds in organic synthesis have been published by Brilkina and Shushunov (1970), by Larock (1978, 1982, 1985), and by Wardell (1988). 

F. R. Jenson and B. Rickborn, Electrophilic Substitution in Organomercurials, McGraw Hill, New York, 1968. 

Coordination chemistry of organomercury(II) involving phenanthrolines, bipyridines, tertiary phos-phines/arsines and some related ligands. T. S. Lobana, Coord. Chem. Rev., 1985,63,161 (186). 

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