Thiyl radical mediated racemization of nonactivated aliphatic amines.
The racemization of nonactivated aliphatic amines has been mediated with alkanethiols and with methyl thioglycolate in the presence of AIBN. The process involves reversible H-abstraction at the chiral center, in a position alpha relative to nitrogen, by thiyl radical. The knowledge of the reaction enthalpy is critical to select the appropriate thiol. In the absence of experimental values, theoretical calculations of the alpha-C-H BDEs and the S-H BDE provide a useful guide.
Escoubet
Stéphanie
S
Laboratoire de Chimie Moléculaire Organique, UMR 6517 "Chimie, Biologie, et Radicaux Libres", Boite 562, Université Paul Cézanne, Aix-Marseille III, Faculté des Sciences St Jérôme, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France.
Gastaldi
Stéphane
S
Vanthuyne
Nicolas
N
Gil
Gérard
G
Siri
Didier
D
Bertrand
Michèle P
MP