Oxidative Amidation of Nitroalkanes with Amine Nucleophiles using Molecular Oxygen and Iodine
Oxidative Amidation of Nitroalkanes with Amine Nucleophiles using Molecular Oxygen and Iodine
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DOI：
10.1002/anie.201505192
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发表时间：
2015-10-26
影响因子：
16.6
通讯作者：
Hayashi, Yujiro
中科院分区：
文献类型：
--
作者：
Li, Jing;Lear, Martin J.;Hayashi, Yujiro
酰胺和肽的形成通常需要强大而温和的试剂系统。然而，所使用的试剂通常是昂贵的和高度复杂的。实现这些目标的新的原子经济和实用的方法是非常可取的。理想地，所述方法应从易于以手性和非手性形式获得的底物开始，并利用与各种各样的官能团、空间位阻和可差向异构的立体中心相容的廉价试剂。在O-2存在下，用I-2和K2 CO 3直接氧化胺与伯硝基烷烃形成酰胺键和肽键。与预期相反，在碘鎓源和胺之间形成1：1卤素键合的络合物，其与硝基膦酸盐反应形成-碘硝基烷烃作为酰胺的前体。
The formation of amides and peptides often necessitates powerful yet mild reagent systems. The reagents used, however, are often expensive and highly elaborate. New atom-economical and practical methods that achieve such goals are highly desirable. Ideally, the methods should start with substrates that are readily available in both chiral and non-chiral forms and utilize cheap reagents that are compatible with a wide variety of functional groups, steric encumberance, and epimerizable stereocenters. A direct oxidative method was developed to form amide and peptide bonds between amines and primary nitroalkanes simply by using I-2 and K2CO3 under O-2. Contrary to expectations, a 1:1 halogen-bonded complex forms between the iodonium source and the amine, which reacts with nitronates to form -iodo nitroalkanes as precursors to the amides.