Predominant role of basicity of leaving group in α-effect for nucleophilic ester cleavage

…, M Horibe, N Mizushima, N Yamamoto, T Takahashi…

Index: Nomura, Yasuo; Kubozono, Takayasu; Hidaka, Makoto; Horibe, Mineko; Mizushima, Naoki; Yamamoto, Nobuyuki; Takahashi, Toshio; Komiyama, Makoto Bioorganic Chemistry, 2004 , vol. 32, # 1 p. 26 - 37

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Citation Number: 12

Abstract

It has been found that α-effects in nucleophilic reactions, unexpectedly large nucleophilicity due to adjacent unpaired electrons, are strongly dependent on the structure of substrate. The nucleophilic cleavages of 4-nitrobenzoate esters and 4-methylbenzoate esters by HOO− have been systematically investigated in detail. When the leaving groups of substrates are sufficiently good (aryl, 2, 2, 2-trifluoroethyl, and 2, 2-dichloroethyl esters), α- ...