Lee Johnny W, Spiegowski Dominique N, Ngai Ming-Yu
Department of Chemistry , Stony Brook University , Stony Brook , New York 11794-3400 , USA . Email:
Institute of Chemical Biology and Drug Discovery , Stony Brook University , Stony Brook , New York 11794-3400 , USA.
Chem Sci. 2017 Sep 1;8(9):6066-6070. doi: 10.1039/c7sc01684k. Epub 2017 Jun 5.
Development of an efficient process that employs commercially available and cost effective reagents for the synthesis of perfluoroalkoxylated aromatic compounds (Ar-OR) remains a daunting challenge in organic synthesis. Herein, we report the first catalytic protocol using readily available perfluoroalkyl iodides (RI) and -(hetero)aryl--hydroxylamides to access a wide range of perfluoroalkoxylated (hetero)arenes. Mild reaction conditions allow for selective O-R bond formation over a broad substrate scope and are tolerant of a wide variety of functional groups. Mechanistic studies suggest the formation and recombination of persistent -hydroxyl radicals and transient radicals under photocatalytic reaction conditions to generate N-OR compounds that rearrange to afford the desired products.
开发一种高效的方法，该方法使用市售且具有成本效益的试剂来合成全氟烷氧基化芳香族化合物（Ar-OR），在有机合成中仍然是一项艰巨的挑战。在此，我们报道了首个催化方案，该方案使用易于获得的全氟烷基碘化物（RI）和 -（杂）芳基-羟酰胺来制备多种全氟烷氧基化（杂）芳烃。温和的反应条件允许在广泛的底物范围内选择性地形成O-R键，并且能够耐受多种官能团。机理研究表明，在光催化反应条件下，持久的羟基自由基和瞬态自由基会形成并重组，生成N-OR化合物，该化合物重排后可得到所需产物。
