Barbier coupling reaction

In essence, the Barbier coupling reaction is a Grignard reaction carried out in situ, although its discovery preceded that of the Grignard reaction by a year. Cf. Grignard reaction. 

Barbier, P. C. R. Hebd. Seances Acad. Sci. 1899, 128, 110. Phillippe Barbier (1848—1922) was bom in Luzy, Nievre, France. He studied terpenoids using zinc and magnesium. Barbier suggested the use of magnesium to his student, Victor Grignard, who later discovered the Grignard reagent and won the Nobel Prize in 1912. 

Moyano, A. Pericas, M. A. Riera, A. Luche, J.-L. Tetrahedron Lett. 1990, 31, 7619. (Theoretical study). 

Name Reactions, 4th ed., DOI 10.1007/978-3-642-01053-8 9, Springer-Verlag Berlin Heidelberg 2009 

Trost and co-workers conducted studies toward the total synthesis of saponaceolide B, an antitumor agent active against 60 human cancer cell lines. One of the challenging structural features of this compound was the cis 2,4-disubstituted 1-methylene-3,3-dimethylcyclohexane ring. The key steps to construct this highly substituted cyclohexane ring were a diastereoselective Barbier reaction to install a vinyl bromide moiety followed by an intramolecular Heck cyclization reaction. 

Stypodiol, epistypodiol and stypotriol are secondary diterpene metabolites produced by the tropical brown algae Stypopodium zonaie. These compounds display diverse biological properties, including strong toxic, narcotic, and hyperactive effects upon the reef-dwelling fish. In the laboratory of A. Abad an efficient stereoselective synthesis of stypodiol and its C14 epimer, epistypodiol, was accomplished from (S)-(+)-carvone. The key transformations in the synthesis of these epimeric compounds were an intramolecular Diels-Alder reaction, a sonochemical Barbier reaction and an acid-catalyzed quinol-tertiary alcohol cyclization. 

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Barbier coupling reaction Metal-mediated addition of alkyl, allyl or benzyl halides to carbonyl compounds. 38... 

Related reactions Barbier coupling reaction, Kagan-Molander samarium diiodide coupling, Nozaki-Hiyama-Kishi reaction ... 

Preparative Methods [difluoro(phenylthio)methyl]trimethyl-silane (PhSCF2SiMe3) was prepared for the first time by Prakash et al., using the Barbier coupling reaction of bromodi-fluoromethylphenyl sulfide, prepared from dibromodifiuoro-methane and sodium benzenethiolate, magnesium metal, and chlorotrimethylsilane (TMSCl) in DMF (eq 1). 

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