Solvomercuration-demercuration

W. Kitching, Organomet. Chem. Rev. 3 61 (1968) R. C. Larock, Solvomercuration/Demercuration Reactions in Organic Synthesis, Springer-Verlag, New bik, 1986. 

Mercury(II) trifluoroacetate is a good electrophile that is highly reactive toward carbon-carbon double bonds [52, 53, 54 When reacting with olefins in nucleophilic solvents, it usually gives exclusively mercurated solvoadducts, but never products of skeletal rearrangement Solvomercuration-demercuration of alkenes with mercury(II) trifluoroacetate is a remarkably effective procedure for the preparation of esters and alcohols with Markovnikov s regiochemistry [52, 55] (equation 24)... 

R. C Larock, Solvomercuration / Demercuration Reactions in Organic Synthesis, Springer, New York (1986), Chpt 3 (review)... 

In 1972, he joined the organic chemistry faculty at Iowa State University, where he is presently University Professor of Chemistry. His early work at Iowa State, on new applications of organomercurials in organic synthesis, earned him an Alfred P. Sloan Foundation Fellowship and a DuPont Young Faculty Scholarship, and culminated in the publication of two books in the area Organomercury Compounds in Organic Synthesis and Solvomercuration/Demercuration Reactions in Organic Synthesis. 

In the first reaction step the enol ether is transformed into an aldehyde. This sequence is named solvomercuration/demercuration. ... 

The former cannot be considered a good synthetic method because a mixture of reaction products is usually obtained. The protonolysis of organomercury compounds has been extensively studied from a mechanistic standpoint but has found little synthetic utility except for isotopic labelling of organic molecules. Reduction is the most useful method for the demercuration of organomercury compounds, particularly of solvomercurials in the solvomercuration-demercuration reaction, and a lot of reductants are used for this purpose. 

The importance of organomercurials in organic synthesis is due in large part to the valuable solvomercuration-demercuration reaction. As the reaction of proton acids with solvomercurated products derived from alkenes leads back to the alkene, protonolysis has in this procedure little synthetic utility. 

Amides.1 The solvomercuration-demercuration of terminal olefins or cyclic olefins with acetonitrile and mercury 11) nitrate followed by reduction of the intermediate organomercury compound affords amides, hydrolyzable to amines. Neither mercuric acetate nor mercuric trifiuoroacetate is satisfactory in this reaction. Preliminary attempts to use a tertiary olefin failed. 

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