Nucleophilicity parameters for amines, amino acids and peptides in water. Variations in selectivities for quinone methides

• Published in: Organic & biomolecular chemistry 2011-10, Vol.9 (19), p.6685-6690
• Main Author: Bentley, T William
• Format: Article
• Language: English
• Subjects: Amines - chemistry; Amino Acids - chemistry; Indolequinones - chemistry; Molecular Structure; Peptides - chemistry; Water - chemistry
• ISSN: 1477-0520; 1477-0539
• DOI: 10.1039/c1ob05715d

Second order rate constants for reactions of 4,4'-dimethylaminobenzhydrylium cations with amines and other nucleophiles in water define a scale of nucleophilicity (N(+)'' = log k + 2.63). The N(+)'' scale can be extended by linking directly to an established N(+) scale based on reactions of methyl vinyl pyridinium cations with amine nucleophiles. Logarithms of rate constants for other benzhydrylium ions and quinone methides (QMs) are correlated by the equation: log k = s(E)N(+)'' + constant, having a nucleophilicity parameter (N(+)'' defined as in the Ritchie N(+) equation with N(+)'' = 4.75 for hydroxide ion), and an electrophile's response (selectivity) parameter (s(E), as in the Swain-Scott equation). Correlations for other benzhydrylium cations require only one slope and one intercept per cation, and fit data for up to 54 amines, amino acids and peptide nucleophiles; the slope s(E) increases as the reactivity of the cation decreases. Contrary to recent reports, s(E) is significantly less than unity for reactions of o- and p-benzoquinone methides. As the reactivities of QMs decrease, s(E) increases and the response of s(E) to changes in reactivity is larger for QMs than for cations.