On the disappearance of the gem-dimethyl effect: the base-catalysed cyclization of ethyl hydantoates†

IB Blagoeva, AJ Kirby, IG Pojarlieff

Index: Atay, Ergun; Blagoeva, Iva B.; Kirby, Anthony J.; Pojarlieff, Ivan G. Journal of the Chemical Society. Perkin Transactions 2, 1998 , # 10 p. 2289 - 2297

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Abstract

Buffer catalysis and solvent kinetic isotope effects in the cyclization of methyl-substituted ethyl hydantoates with ω-N-methyl (MUE) and ω-N-phenyl groups (PUE) have been studied in an attempt to elucidate the changes in mechanism and eventual reversal of relative reactivities caused by increasing the number of substituent methyl groups (the gem-dimethyl effect).(Rate constants for the hydroxide-catalysed cyclization are actually reduced on ...