title: The syn-oriented 2-OH provides a favorable proton transfer geometry in 1,2-diol monoester aminolysis: implications for the ribosome mechanism.
abstract: A computational study of 1-formyl 1,2-ethanediol aminolysis predicts a stepwise mechanism involving syn-2-OH-assisted proton transfer. The syn-oriented 2-OH takes over the catalytic role of the external water or amine molecule previously observed in 2-deoxy ester aminolysis. It provides more favorable, that is, more linear, proton transfer geometry for the rate-limiting transition state resulting in an almost billion-fold rate acceleration of the overall reaction. These findings provide structural basis for explanation of the efficiency of the proton shuttling mechanism and imply double proton transfer catalysis by peptidyl tRNA A76 2'-OH as a possible catalytic strategy used by ribosome.
authors.affiliation: Laboratory of BioCatalysis, Institute of Organic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria.
authors.forename: Miroslav A
authors.initials: MA
authors.lastname: Rangelov
authors.forename: Georgi N
authors.initials: GN
authors.lastname: Vayssilov
authors.forename: Vihra M
authors.initials: VM
authors.lastname: Yomtova
authors.forename: Dimiter D
authors.initials: DD
authors.lastname: Petkov
mesh_terms: D000588:Amines / Q000737:chemistry; D019855:Ethylene Glycol / Q000737:chemistry*; D008968:Molecular Conformation; D012343:RNA, Transfer / Q000737:chemistry; D012270:Ribosomes / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D000588:Amines; D012343:RNA, Transfer; D019855:Ethylene Glycol