Naslov
Deprotonation of Enoxy Radicals: Theoretical Validation of a 50-Year-Old Mechanistic Proposal

Autori
Smith, David Matthew ; Buckel, Wolfgang ; Zipse, Hendrik

Izvornik
Angewandte Chemie. International edition (1433-7851) 42 (2003), 16; 1867-1870

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
ab initio calculations ; acidity ; C-H activation

Sažetak
Almost 50 years ago, Sir John W. Cornforth suggested that an enoxy radical (derived by a-H-atom abstraction in a mechanism similar to that proposed for the dehydration of 4-hydroxybutyryl-CoA) might undergo facile deprotonation to a ketyl radical anion. However, this suggestion has not since been proven by any experimental or theoretical data. Herein, we aim to quantify the acidity of the b position of the enoxy radical. We wish to determine whether the acidity of this radical is sufficiently enhanced over the closed-shell thioester to explain the apparent deprotonation at the unactivated position, or whether additional factors must be invoked to arrive at a satisfactory mechanism.

Izvorni jezik
Engleski

Znanstvena područja
Kemija, Biologija

POVEZANOST RADA