Deprotonation of Enoxy Radicals: Theoretical Validation of a 50-Year-Old Mechanistic Proposal (CROSBI ID 130222)
Prilog u časopisu | izvorni znanstveni rad | međunarodna recenzija
Podaci o odgovornosti
Smith, David Matthew ; Buckel, Wolfgang ; Zipse, Hendrik
engleski
Deprotonation of Enoxy Radicals: Theoretical Validation of a 50-Year-Old Mechanistic Proposal
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.
ab initio calculations ; acidity ; C-H activation
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Podaci o izdanju
42 (16)
2003.
1867-1870
objavljeno
1433-7851
1521-3773
10.1002/anie.200250502