Do General Nucleophilicity Scales Exist?

J. Phys. Org. Chem., 2008, 21, 584–595 published on 21.05.2008
J. Phys. Org. Chem.

Comprehensive nucleophilicity scales including π-, n- and σ-nucleophiles have been constructed using benzhydrylium ions and structurally related quinone methides as reference electrophiles. It is shown how the correlation (Eqn (1)) log k_(20°C) = s(E + N), where s and N are nucleophile-specific parameters and E is an electrophile-specific parameter, has recently been employed to characterize further classes of nucleophiles (phosphines, amines, isonitriles, trifluoromethanesulfonyl-substituted carbanions) and electrophiles (2-benzylideneindan-1,3-diones and benzylidenebarbituric acids). Practical applications of the reactivity parameters E, N and s for developing Friedel–Crafts alkylations in neutral alcoholic or aqueous solution and for characterizing nucleophilic organocatalysts will be discussed. Eventually, a new correlation equation will be presented, which includes Eqn (1), the Ritchie equation (nucleophilic additions to stabilized carbocations), and the Swain–Scott equation (nucleophilic substitutions of methyl halides) as special cases.

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