Concerted Grob Fragmentation in N-Halo-α-amino Acid Decomposition

Article abstract of DOI:10.1021/jo00095a048

The Grob fragmentation of N-halo-α-amino acids in aqueous solution has been studied, being first order in N-halo-α-amino acid and pH-independent.The substituents on the C₂ and N atoms strongly affect the reaction rate.Structure reactivity correlations for C₂ substituents provide ρ^* values of -3.9 and -4.1 for N-Cl and N-Br compounds, respectively.The same correlations for N substituents lead to ρ^* values of -2.1 and -1.9 for N-Cl and N-Br compounds.The transition state (TS) can be generally described as product-like, its structure and characteristics being significantly affected by the substituents on the C₂ and on the N atoms.In conclusion, the reaction is a D_ED_N concerted and slightly nonsynchronous two-stage process.