Copper-catalyzed group-transfer reactions transfers

The seminal report of an asymmetric homogeneous metal-catalyzed reaction described the copper-catalyzed group-transfer reaction from a diazoester to an alkene, Eq. 3 (2). This article provided experimental verification of the intervention of copper carbenoid olefin complexes in the catalytic decomposition of diazo com-... 

This chapter will begin with a discussion of the role of chiral copper(I) and (II) complexes in group-transfer processes with an emphasis on alkene cyclo-propanation and aziridination. This discussion will be followed by a survey of enantioselective variants of the Kharasch-Sosnovsky reaction, an allylic oxidation process. Section II will review the extensive efforts that have been directed toward the development of enantioselective, Cu(I) catalyzed conjugate addition reactions and related processes. The discussion will finish with a survey of the recent advances that have been achieved by the use of cationic, chiral Cu(II) complexes as chiral Lewis acids for the catalysis of cycloaddition, aldol, Michael, and ene reactions. 

Copper-catalyzed cross-couplings between unactivated alkyl halides and organomagne-sium compounds have been known since the late 1960s and probably are the most studied alkyl-alkyl coupling reactions. The main drawback of this protocol was the need of stoichiometric amounts of copper salts for the formation of the organocuprate, and consequently this led to loss of 1 equiv. of the non-transferred alkyl group. 

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