Rate constants for 1,n-hydrogen transfer reactions in some amino acid derived radicals

Absolute rate constants for l,n-hydrogen atom transfers in some substituted amino acid derived radicals have been determined in benzene through the use of competitive kinetic experiments. Radicals derived from methyl N-(2-iodobenzoyl)-N-(tertbutyloxycarbonyl)glycinate, -alaninate, -leucinate, -tert-leucinate and -phenylglycinate undergo intramolecular 1,5-hydrogen atom transfer to afford the corresponding alpha-amino acid ester radicals with rate constants in the range: 1.0-4.3 x 10(7) s(-1) at 80 degrees C. Where abstractable hydrogen atoms exist in the amino acid side-chain, 1,6- and 1,7-translocations are competitive processes. (c) 2006 Elsevier Ltd. All rights reserved.