Nucleophilic Substitution on Csp3 Carbon Atoms

The functionalization of aromatic compounds through catalytic stereoselective reactions is predominant in modern organic chemistry, and constitutes the leitmotiv in approaching new complex chiral molecules. In this framework, asymmetric Friedel-Crafts alkylations, based on nucleophilic substitution of pro-stereogenic Csp3 carbon atoms are becoming of great importance. In this chapter, we present and overview of the works published in this scenario, with particular concern to the selective ring-opening of enantiomerically pure epoxides via mild Lewis acids catalysis, kinetic resolution of chiral racemic cis and trans oxiranes and desymmetrization of meso with indoles and chiral organometallic catalysis. The emerging field of direct activation of alcohols in sterecontrolled FC alkylations is also matter of discussion. Both diastereo- and enantioselective approaches are described. Here, particular emphasis has been devoted to the peculiar attitude of ferrocenyl alcohols in participating in catalytic alkylations of arenes “on water”.