Mechanisms of Copper-mediated Addition and Substitution Reactions

Mechanisms of Copper-mediated Addition and Substitution Reactions 

Organocopper chemistry is still rapidly expanding its synthetic scope. The scope of carbocupration, previously limited to acetylenes, has recently been extended to olefins [33-36]. 1,6-, 1,8-, 1,10-, and 1,12-Addition and 1,5-5 2 substitution reac- 

Two sources of mechanistic information, new analytical and new theoretical methods, have surfaced in the past several years. The former class includes new methods in the study of kinetic isotope effects, in NMR spectroscopy, and in X-ray 

Three important categories of copper reactions - conjugate addition, carbocupra-tion, and alkylation - are discussed. 

Two sources of ruedianistic inforn ruetliods, have surfaced in die past ruetliods in tlie study of kinetic isoto  

Fout-cenieted addition of RCu to an enone was widely discussed in tlie 1960s iSclieme 10.3a) [51-53], wb de discussions on six-centered ttansition states have continued imt d recent times iSclieme 10.3b) [54], Hiese meclianisms do not, bowevet, explain tbe fotciiation of E/Z mixtures of enolate stereoisomers [20, 55] and must now be considered obsolete. 

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I 70 Mechanisms of Copper-mediated Addition and Substitution Reactions... 

Mori, S. Nakamura, E. Mechanisms of Copper-mediated Addition and Substitution Reactions. In Modem Organocopper Chemistry, Krause, N., Ed. Wiley-VCH Weinheim, 2002 pp 315-346. 

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