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Nucleophilic Reactivities of Ketene Acetals
Author(s) -
Tokuyasu Takahiro,
Mayr Herbert
Publication year - 2004
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200400134
Subject(s) - ketene , chemistry , electrophile , nucleophile , reactivity (psychology) , reaction rate constant , computational chemistry , kinetics , ion , medicinal chemistry , photochemistry , organic chemistry , catalysis , medicine , physics , alternative medicine , pathology , quantum mechanics
The kinetics of the reactions of ketene acetals with benzhydrylium ions have been followed photometrically. The reactions proceed with rate‐determining C−C bond formation that is considerably faster than expected for outer‐sphere electron transfer processes. Structure−reactivity relationships are discussed. The excellent correlations between the observed second‐order rate constants (log k 2 ) and the previously reported electrophilicity parameters ( E ) of benzhydrylium ions suggest that several of the compounds investigated in this work can be used as reference nucleophiles for the development of electrophilicity scales. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)