Efficient intramolecular general acid catalysis of the reactions of αeffect nucleophiles and ammonia oxide on a phosphate triester                         !"    #"   University Chemical Laboratory, Cambridge CB2 1EW, UK.  Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, 88040)900, Brazil. ajk1@cam.ac.uk ; faruk@qmc.ufsc.br Electronic Supporting Information Contents. 1. Identification of succinic acid produced by diimide reduction of fumarate (paper, Scheme 3). Scheme S.1 The reaction scheme. 1 H NMR experiments. Charts S.1.1, S. 1.2 Chemical shifts and signal assignments for the succinic acid identification GCMS analysis. Figures S.1, A, B and C Chromatograms Figures S.2, A and B Fragmentation patterns 2. Kinetic results Figure S.3 Brønsted plots comparing reactions of hydroxylamines with triesters 1.H + and diethyl 2,4)dinitrophenyl phosphate. Table S.1. First order rate constants for the reactions of hydroxylamines with triester 1.H + as a function of pH, in water at 60°C and ionic strength 1.0 M (KCl). Table S.2. Second order rate constants for the reactions of hydroxylamines with triester 1.H + as a function of temperature, in water at ionic strength 1.0 M (KCl). Table S.3. Derived activation parameters for the reactions of hydroxylamines with triester 1.H +  3. Calculational results Table S.4. Cartesian Coordinates for the calculated (C)PCM)HF 6)31G(d,p)) structure of triester 1.H + . Table S.5. Cartesian Coordinates from the calculated (C)PCM)HF 6)31G(d,p) structure of ammonia oxide. Table S.6. Cartesian Coordinates from the calculated (C)PCM)HF 6)31G(d,p) ) transition state for the reaction of ammonia oxide with triester (Figure 3).