Reactivities of amino acid derivatives toward hydrogen abstraction by Cl• and OH•.
In recent computational studies of hydrogen-atom abstraction from amino acid derivatives, two distinct rationalizations have been put forward for the relative inertness of the α-C-H. Of these, the proposal that the inertness is due to a "kinetic trap" associated with particularly stable complexes is shown to be unlikely because of unfavorable entropies. On the other hand, the proposed existence of deactivating polar effects at the α-position in Cl(•) abstractions is likely also to be applicable to OH(•) abstractions, but to a lesser extent.
School of Chemistry, University of Sydney, Sydney, New South Wales 2006, Australia. chan_b@chem.usyd.edu.au
Bun
B
Chan
Robert J
RJ
O'Reilly
Christopher J
CJ
Easton
Leo
L
Radom
D000596:Amino Acids / Q000737:chemistry*; D002713:Chlorine / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D006878:Hydroxides / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism
D000596:Amino Acids; D006878:Hydroxides; D002713:Chlorine; D006859:Hydrogen