π-Nucleophilicity in Carbon−Carbon Bond-Forming Reactions

Which electrophiles react with which nucleophiles? The correlation log k(20 degrees Celsius) = s(E + N), in which electrophiles (carbocations, metal-pi-complexes, diazonium ions) are characterized by one (E) and nucleophiles are characterized by two parameters (N, s), proved to be applicable for a wide variety of electrophile-nucleophile combinations. Since the introduction of this correlation in 1994 (Angew. Chem., Int. Ed. Engl. 1994, 33, 938-957), numerous new reagents have been characterized, and in 2001 (J. Am. Chem. Soc. 2001, 123, 9500-9512), a new method of parametrization was proposed that facilitates a continuous extension of the data sets without the need for reparametrization of existing data. This…