Photosensitized Intermolecular Carboimination of Alkenes through the Persistent Radical Effect

Abstract

An intermolecular, two‐component vicinal carboimination of alkenes has been accomplished by energy transfer catalysis. Oxime esters of alkyl carboxylic acids were used as bifunctional reagents to generate both alkyl and iminyl radicals. Subsequently, addition of the alkyl radical to an alkene generates a transient radical for selective radical–radical cross‐coupling with the persistent iminyl radical. Furthermore, this process provides direct access to aliphatic primary amines and α‐amino acids by simple hydrolysis.

Oxime‐Derived Iminyl Radicals in Selective Processes of Hydrogen Atom Transfer and Addition to Carbon‐Carbon π‐Bonds

“…In addition, synthetic potential of some types of iminyl radicals reactivity, such as intermolecular NÀ O and NÀ N coupling is still to be realized for oxime-derived iminyl radicals. [55,56,[161][162][163][164]…”

Thioxanthone: a powerful photocatalyst for organic reactions

“…86 Investigating the synthetic utility of a novel oxyamination strategy, they reported a metal-free regioselective oxyimination addition to unactivated alkenes (Scheme 22). Based on their previous reports, 87 Glorius and coworkers envisioned that oxime esters could be excellent candidates for the simultaneous generation of both Nand Ocentered radicals. For this reason, they studied the reaction of several benzophenone oxime esters 87 with 1-octene.…”

Synthesis of Azetidines via Visible Light-Mediated Intermolecular [2+2] Photocycloaddition

“…Triplet state oximes have recently been utilized to generate iminyl radicals in the context of alkene or arene functionalization. 28,29 In contrast, their reactivity has not yet been explored to achieve [2+2] photocycloadditions, likely due to their preference to undergo E/Z isomerization or N-O bond cleavage reactions ( Fig. 1B).…”