Organomercury compounds synthesis

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

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). 

It is difficult to establish to what extent methyl mercury residues found in the environment arise from natural as opposed to human sources. There is no doubt, however, that natural generation of methyl mercury makes a significant contribution to these residues. Samples of Tuna fish caught in the late 18th century, before the synthesis of organomercury compounds by humans, contain significant quantities of methyl mercury. 

R. C. Larock, Organomercury Compounds in Organic Synthesis, Springer-Verlag, Berlin, 1985. 

Other Cyclopropanation Methods. Haloalkylmercury compounds are also useful in synthesis. The addition reactions are usually carried out by heating the organomercury compound with the alkene. Two typical examples are given in Section C of Scheme 10.9. 

Then he swiftly produced as many different varieties of the compounds as possible, including dimethylzinc, which convinced other scientists to accept Avogadro s theory, a foundation of atomic chemistry and methyl-mercury iodide, the first of many organomercury compounds known to poison people who eat mercury-contaminated fish. Despite his skill at synthesis, Frankland did not discover tetraethyl lead, the gasoline additive that became one of the most important industrial compounds of the mid-twentieth century (Chapter 6). 

R. C. Mehrotra and R. Bohra, Metal Carboxylates. Academic Press, London, 1983. 5a. R. C. Larock, Organomercury Compounds in Organic Synthesis, p. 101. Springer-... 

Metathesis reactions continue to be extensively employed in the synthesis of organomercury compounds. While most reactions involve the use of organolithium or Grignard reagents, other organometallic compounds are sometimes used as starting materials. 

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... 

For reviews, see Larock Organomercury Compounds in Organic Synthesis Springer New York. 1985. pp. 60-97 Wardell, in Zuckerman, Ref. 246. pp. 308-318. 

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. 

Hundreds of reports have been published on electrophilic mercuration of a variety of aromatic compounds and uses of the resulting organomercurials in synthesis [5, 7-11]. Although in this chapter, we will not discuss synthetic applica-... 

Thus, the synthesis of triphenylscandium is a salt-elimination reaction (or metathesis) whilst the route for the lanthanide phenyls involves a redox reaction. The former has the problem of producing LiCl, which is often significantly soluble in organic solvents and contaminates the desired product, whilst the latter involves disposal of mercury waste, as well as handling toxic organomercury compounds. 

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