Jiao Jiwen, Wang Xiaoming
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou, 310024, China.
Angew Chem Int Ed Engl. 2021 Jul 26;60(31):17088-17093. doi: 10.1002/anie.202104359. Epub 2021 Jun 22.
Amides are essentially inert carboxyl derivatives in many types of chemical transformations. In particular, deoxygenative C-C bond formation of amides to synthetically important amines is a long-standing challenge for synthetic chemists due to the inertness of the resonance-stabilized amide C=O bond. Herein, it is disclosed that by merging electron-transfer-induced activation with 1,2-metalate rearrangement, a wide range of aromatic amides react smoothly with arylboron reagents, affording a series of biologically relevant diarylmethylamines as deoxygenative C-C bond cross-coupling products. With its simplicity and versatility, this reaction shows great promise in the synthesis of amines from amides, which may open up new avenues in retrosynthetic planning and find widespread use in academia and industry.
在许多类型的化学转化中，酰胺基本上是惰性的羧基衍生物。特别是，由于共振稳定的酰胺C=O键的惰性，将酰胺进行脱氧C-C键形成以合成重要的胺类，长期以来一直是合成化学家面临的挑战。在此，据披露，通过将电子转移诱导活化与1,2-金属酸盐重排相结合，多种芳香族酰胺能与芳基硼试剂顺利反应，得到一系列具有生物学相关性的二芳基甲胺作为脱氧C-C键交叉偶联产物。该反应因其简单性和通用性，在从酰胺合成胺类方面显示出巨大潜力，这可能为逆合成规划开辟新途径，并在学术界和工业界得到广泛应用。
