Oxime‐Ether Group Transfer to Unpolarized C(sp3)─H Bonds via Light‐Induced HAT Catalysis

This study introduces a sustainable and efficient method for direct alkane to oxime-ether functionalization via light-induced hydrogen-atom transfer (HAT) catalysis. Featuring low catalyst loadings, broad substrate scope, sunlight compatibility, and scalable synthesis, the protocol achieves selective C(sp³)─H functionalization without directing groups. Mechanistic insights reveal a radical pathway, emphasizing the method's potential in synthesizing pharmacologically and industrially relevant oxime-ethers under mild, oxidant-free conditions.

Abstract

In this study, we demonstrate an effective method for the direct conversion of alkane chemical feedstocks to valuable oxime-ethers through the functionalization of unpolarized C(sp³)─H bonds using light-induced HAT-catalysis. The process operates at room temperature, utilizing low catalyst loading (ppm level) and a reduced substrate-to-reagent ratio. Notably, the reaction can also be performed in sunlight, which makes the process further attractive toward sustainable synthesis of functionalized oxime-ethers. The process displays a broad substrate scope, rendering desired products with up to 90% yields. The reaction is shown to be scalable. Through a series of mechanistic control studies, a radical reaction pathway featuring HAT-induced C─H functionalization is implicated in the process.

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