Mercury acetate, reaction with alkene

In the laboratory, alkenes are often hydrated by the oxymercuration-demercuration procedure. Oxymercuration involves electrophilic addition of Hg2+ to the alkene on reaction with mercury(II) acetate [(CH3C02)2Hg, often abbreviated Hg(OAc)2] in aqueous tetrahydrofuran (THF) solvent. When the intermediate organomercury compound is then treated with sodium borohydride, NaBH4, demercuration occurs to produce an alcohol. For example ... 

Perlmutter used an oxymercuration/demercuration of a y-hydroxy alkene as the key transformation in an enantioselective synthesis of the C(8 ) epimeric smaller fragment of lb (and many more pamamycin homologs cf. Fig. 1) [36]. Preparation of substrate 164 for the crucial cyclization event commenced with silylation and reduction of hydroxy ester 158 (85-89% ee) [37] to give aldehyde 159, which was converted to alkenal 162 by (Z)-selective olefination with ylide 160 (dr=89 l 1) and another diisobutylaluminum hydride reduction (Scheme 22). An Oppolzer aldol reaction with boron enolate 163 then provided 164 as the major product. Upon successive treatment of 164 with mercury(II) acetate and sodium chloride, organomercurial compound 165 and a second minor diastereomer (dr=6 l) were formed, which could be easily separated. Reductive demercuration, hydrolytic cleavage of the chiral auxiliary, methyl ester formation, and desilylation eventually led to 166, the C(8 ) epimer of the... 

Oxymercuration-reduction of alkenes preparation of alcohols Addition of water to alkenes by oxymercuration-reduction produces alcohols via Markovnikov addition. This addition is similar to the acid-catalysed addition of water. Oxymercuration is regiospecific and auft -stereospecific. In the addition reaction, Hg(OAc) bonds to the less substituted carbon, and the OH to the more substituted carbon of the double bond. For example, propene reacts with mercuric acetate in the presence of an aqueous THF to give a hydroxy-mercurial compound, followed by reduction with sodium borohydride (NaBH4) to yield 2-propanol. 

A mild and highly convenient procedure for the hydration of a carbon-carbon double bond involves the initial reaction of an alkene with mercury(n) acetate in aqueous tetrahydrofuran, the resulting mercurial intermediate is reduced in situ by alkaline sodium borohydride solution. The yields of alcohols which are... 

Sometimes the reaction conditions used in this reaction are too harsh since heating is involved and rearrangement reactions can occur. A milder method that gives better results is to treat the alkene with mercuric acetate [Hg(OAc)2] then sodium borohydride. The reaction involves electrophilic addition of the mercury reagent to form an intermediate mercuronium ion. This reacts with water to give an organomercury intermediate. Reduction with sodium... 

In contrast to lead tetraacetate, simple addition to the double bond does not occur as a side re-action. While allylic rearrangement is common and mixtures of products are frequently obtained, the reaction often proceeds in very high yield and is simple to carry out the alkene is simply heated in an appropriate solvent with mercury(II) acetate until reaction is complete. Mercury(II) acetate has also been us for dehydrogenation, particularly in the steroid field. One interesting example incorporating simultaneous dehydrogenation and allylic oxidative rearrangement is seen in the reaction of abietic acid (37 equation 16). ... 

Vicinal hydroxy carbamates are prepared by the osmium-catalyzed reaction of alkenes with A-chloro-A-metallocarbamates generated in situ from A-chloro-A-sodiocarbamates (easily prepared from the carbamate, tert-butyl hypochlorite, and sodium hydroxide in methanol) by reaction with silver nitrate77 or mercury(II) salts78 in acetonitrile, The greatest reactivity was, however, displayed by the A-chloro-A-sodiocarbamate/mercuryUI) nitrate/tetraethylam-monium acetate (relative ratio 1.5 0.75 1) system, unfortunately low yields of hydroxycarba-mates from trisubstituted alkenes were obtained, due to competitive formation of organomer-... 

A number of metals salts can be used as the source of electrophiles in reactions with alkenes. One of the most interesting of these involves the attack of mercury(II) acetate in acetic acid. Reductive cleavage of the organomercury compound with sodium borohydride leads to the overall hydration of the alkene in a Markownikoff sense. There are a number of preparative advantages, such as a reduced tendency to rearrange, associated with this and similar relatively mild procedures when compared to the direct protonation of a double bond (Scheme 3.14)... 

Treatment of an alkene with mercuric acetate in aqueous THF results in the electrophilic addition of mercuric ion to the double bond to form an intermediate mercuri-um ion. Nucleophilic attack by H2O at the more substituted carbon yields a stable organomercury compound, which upon addition of NaBH4 undergoes reduction. Replacement of the caiton-mercury bond by a carbon-hydrogen bond during the reduction step proceeds via a radical process. The overall reaction represents Markovnikov hydration of a double bond, which contrasts with the hydroboration-oxidation process. 

Alkyl phenyl sulfones (piCj,27) are nearly as acidic as esters hence they are readily deprotonated by n-BuLi, LDA in THF, or EtMgBr in THF to give a-metalated sulfones. Their reaction with aldehydes gives a mixture of diastereomeric P-phenylsul-fone alkoxide adducts. Reductive elimination of the benzenesulfinate moiety from the adduct to produce the alkene is usually slow. To minimize side reactions, the hydroxyl group is first converted to an acetate, benzoate, mesylate, or /7-toluenesul-fonate and then treated with an excess of sodium amalgam [Na(Hg), prepared by adding small pieces of sodium to mercury] in methanol to furnish the trans-dlk n P... 

Mercury salts have previously been shown to be capable of cleaving cyclopropyl bonds. Phenyl-substituted cyclopropanes react with mercury(II) acetate to give 3-mercurio-l-methoxy-l-phenylpropane derivatives, which can undergo further reactions such as reduction with sodium borohydride or addition to alkenes. For example, treatment of phenyl-cyclopropane (1) with mercury(II) acetate in methanol, followed by the addition of sodium chloride, produced 3-(chloromercurio)-l-methoxy-l-phenylpropane(2) in good yield.When the primary mercury adduct was reacted with alkenes without isolation, the yields were lower than those in the two-step transformation. ... 

Cyclopropyl trimethylsilyl ethers, which were readily prepared from aldehydes, ketones and esters, coupled with alkenes on treatment with mercury(II) acetate and, after reduetion with sodium borohydride, afforded chain-extended carbonyl compounds, e.g. 37, in moderate to good yields. The whole reaction could be carried out in one pot. 

The reaction is performed in two operations, the first of which is oxymercuration. In this stage the alkene is treated with mercury(II) acetate [Hg(02CCH3)2, abbreviated as Hg(OAc)2]. Mercury(II) acetate is a source of the electrophile HgOAc, which bonds to C-1 of the alkene. The oxygen of water, one of the components in the THF-H2O solvent mixture, bonds to C-2. The demercuration operation uses sodium borohydride (NaBH4, a reducing agent) to convert C—Hg to C—H. 

The reaction of an alkene with an alcohol in the presence of a mercury salt such as mercuric acetate or trifluoroacetate leads to an alkoxymercury intermediate, which on reaction with sodium borohydride yields an ether. 

Oxymercuration occurs with an alkyne as with an alkene, but differences in reactivity lead to a modification in the procedure. For reasons that will not be discussed, a mixture of mercuric sulfate (HgS04) and mercuric acetate [Hg(OAc)2] is used. When 1-heptyne is treated with this mixture in aqueous solvent, the initially formed enol (107) tautomerizes to 2-heptanone (108), which is isolated in 80% yield. Note that the ketone product mentioned in connection with vinyl chloride 92 in Section 10.4.5 results from formation of an enol. There is an important difference in the oxymercuration of alkynes and alkenes that is notable in this transformation. The mercury reacts with the alkyne, but the mercury is lost when the enol is formed and there is no need to add NaBH in a second step. This observation is general for oxymercuration of alkynes under these conditions. The more stable secondary vinyl carbocation is an intermediate, but the vinyl-mercury compound formed by reaction with the carbocation is unstable in the presence of water, so the enol is the product. 

Electrophilic Addition to Alkenes, Hydroxy- and alkoxymercurations of alkenes have been performed in micellar SDS. Hydroxymercuration of (1) with mercury(II) acetate, followed by reduction with sodium borohydride, gave a greatly enhanced yield of (2) in micellar SDS (90%) relative to that obtained in THF-H2O (20-25%) (eq 2). Also, the reactions of (1) and the related limonene gave greater cyclic ether diol product ratios in the SDS environment than in aq THF. Both the enhanced 3delds and ratios were attributed to anisotropic solubilization of the alkylmercurial intermediate in a relatively H2O poor mIceUar microenvironment. The hydroxymercuration of an aromatic diene, /Mliallylbenzene, did not display enhanced chemoselectivlty (mono vs. diol formation) in micellar SDS relative to that obtained in THF-H2O. This result suggests that the mIceUar solubilization sites of aromatic substrates and reaction intermediates are more HzO-rich than those of aliphatic systems. 

In an oxymercuration-demercuration reaction, an alkene is treated with mercury(II) acetate, Hg(OAc)2, and the product is treated with sodium borohydride. The net result is a Markovnikov addition product in which the OH group bonds to the more substituted carbon atom of the alkene. 

An alternative method of Markovnikov addition of water to alkenes involves an intermediate rather similar to the bromonium ion. This is a mercurinium ion, formed by the reaction of an alkene with mercury (II) acetate (check out the sizes of mercury and bromine, and you will see why these are so similar). This is often preferred to acid-catalyzed hydration, as conditions... 

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