Repurposing trichloroacetonitrile as a sustainable radical synthon for regiodivergent photocatalytic alkene amination

Abstract

Persistent endeavors have been dedicated to the synthesis of nitrogen-containing compounds, which hold paramount significance in biological processes and are indispensable in the realms of pharmaceuticals and advanced materials. Herein, an innovative photocatalytic radical relay strategy has been devised for the regiodivergent amination of alkenes utilizing trichloroacetonitrile (CCl₃CN) as an N-centered radical precursor, diverging from its classical electrophilic reactivity. This method leveraged the inherent weakness of the N–O bond in an oxime-imidate reagent to generate electrophilic amidyl radicals via oxy-radical isomerization, without gaseous byproducts, and enabling three distinctive amination pathways: 1,2-diamination, a three-component radical-relay assembly of 1,4-diamines from two distinct olefins, and anti-Markovnikov hydroamination of alkenes. The CCl₃ group plays a pivotal role in modulating the reactivity of amidyl radical intermediates through its electron-withdrawing effects, while also demonstrating compatibility with further functionalization via boryl radical chemistry. This work repositions a legacy electrophile as a multifaceted radical synthon, offering a general strategy for modular nitrogen incorporation in complex molecule synthesis.