Revealing the Iron-Catalyzed β-Methyl Scission of tert-Butoxyl Radicals via the Mechanistic Studies of Carboazidation of Alkenes.

ABSTRACT: We describe here a mechanistic study of the iron-catalyzed carboazidation of alkenes involving an intriguing metal-assisted β-methyl scission process. Although t-BuO radical has frequently been observed in experiments, the β-methyl scission from a t-BuO radical into a methyl radical and acetone is still broadly believed to be thermodynamically spontaneous and difficult to control. An iron-catalyzed β-methyl scission of t-BuO is investigated in this work. Compared to a free t-BuO radical, the coordination at the iron atom reduces the activation energy for the scission from 9.3 to 3.9 ~ 5.2 kcal/mol. The low activation energy makes the iron-catalyzed β-methyl scission of t-BuO radicals almost an incomparably facile process and explains the selective formation of methyl radicals at low temper

SUBMITTER: Chiou MF 

PROVIDER: S-EPMC7179474 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature