The alkoxyl radical is an essential reactive intermediate in mechanistic studies and organic synthesis with hydrogen atom transfer (HAT) reactivity. However, compared with intramolecular 1,5-HAT or intermolecular HAT of alkoxyl radicals, the intramolecular 1,2-HAT reactivity has been limited to theoretical studies and rarely synthetically utilized. Here we report the first selective 1,2-HAT of alkoxyl radicals for α-C(sp³)-H bond allylation of α-carbonyl, α-cyano, α-trifluoromethyl, and benzylic N-alkoxylphthalimides. The mechanistic probing experiments, electron paramagnetic resonance (EPR) studies, and density functional theory (DFT) calculations confirmed the 1,2-HAT reactivity of alkoxyl radicals, and the use of protic solvents lowered the activation energy by up to 10.4 kcal/mol to facilitate the α-C(sp³)-H allylation reaction.

烷氧基是机械研究和具有氢原子转移（HAT）反应性的有机合成中必不可少的反应中间体。但是，与分子内的1，5-HAT或分子间的烷氧基的HAT相比，分子内的1，2-HAT的反应性仅限于理论研究，很少用于合成。在这里，我们报告了α-羰基，α-氰基，α-三氟甲基和苄基N-烷氧基邻苯二甲酰亚胺的α-C（sp ³）-H键烯丙基化的烷氧基的第一个选择性1,2-HAT 。机械探测实验，电子顺磁共振（EPR）研究和密度泛函理论（DFT）计算证实了烷氧基的1,2-HAT反应性，并且质子溶剂的使用使活化能降低了10.4 kcal / mol。促进α-C（sp³）-H烯丙基化反应。