Carbanion photochemistry. 2. Kinetic control of product formation in reactions of radicals with carbanions
作者:Laren M. Tolbert
DOI:10.1021/ja00530a037
日期:1980.5
The interaction of resonance-stabilized carbanions with methyl radicals produced by the irradiation of the carbanions in dimethyl sulfoxide is governed by the pK/sub a/ of the carbanion conjugate acid to a greater extent than by the stability of the resulting radical anion. This kinetic effect is explained using energetic considerations based on the Hammond postulate and is further rationalized by
Nucleophilic cleavage of 2,2-dimethylaziridines: competition between SN2 and postulated “SET” mechanism.
作者:H. Stamm、P. Assithianakis、B. Buchholz、R. Weiβ
DOI:10.1016/s0040-4039(00)85562-8
日期:1982.1
Regioselectivity of nucleophilic attack on 2,2-dimethylaziridines depends on the degree of leaving group activation: in highly activated aziridines it occurs at the methylene carbon and in less activated at the tertiary carbon. This latter abnormalringopening is explained by an SET mechanism.