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Transition Metal Free Catalytic Aerobic Oxidation of Alcohols Under Mild Conditions Using Stable Nitroxyl Free Radicals

机译:使用稳定的硝基吡咯基团在温和条件下的醇的过渡金属无菌催化氧化醇

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The oxidation of alcohols to the corresponding aldehydes, ketones or acids represents one of the most important functional group transformations in organic synthesis. While this is an established reaction, it still presents an important challenge (1). Although there are numerous oxidation methods reported in the literature, only a few describe the selective oxidation of primary or secondary alcohols to the corresponding aldehydes or ketones utilizing TEMPO based catalyst systems in combination with clean oxidants such as O_2 and H_2O_2 (2). The most efficient, common, TEMPO based systems require the use of substantial amounts of expensive and/or toxic transition metal complexes, which makes them unsuitable for industrial scale production. Here, we report a highly effective aerobic oxidation of primary and secondary alcohols by a catalyst system, based on 4-acetamido-2,2,6,6-tetramethylpiperidin-1-oxyl (AA TEMPO), Mg(N0_3)_2 and N-bromosuccinimide (NBS) in an acetic acid solvent.
机译:醇对相应的醛,酮或酸的氧化是有机合成中最重要的官能团转化之一。虽然这是一个既定的反应,但它仍然存在重要挑战(1)。虽然文献中报道了许多氧化方法,但仅利用节点基催化剂体系与诸如O_2和H_2O_2(2)的清洁氧化剂的组合,仅描述对相应的醛或酮的相应醛或酮的选择性氧化。最有效,常见的基于节奏的系统需要使用大量的昂贵和/或有毒的过渡金属配合物,这使得它们不适合工业规模生产。在此,我们通过催化剂体系报告了一种高效的初级和仲醇的有氧氧化,基于4-乙酰氨基-2,2,6,6-四甲基哌啶-1-氧基(AA Tempo),Mg(NO_3)_2和n -Broom琥珀酰亚胺(NBS)在乙酸溶剂中。

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