Nature Communications ( IF 14.7 ) Pub Date : 2020-09-23 , DOI: 10.1038/s41467-020-18593-4 Lei Li 1 , Min Yang 2 , Qiuqin He 1 , Renhua Fan 1
Insertion of atoms into aromatic carbon-nitrogen bonds is an appealing method for the synthesis of nitrogen-containing molecules and it has the advantage of the availability and abundance of anilines. However, the direct cleavage of aromatic carbon-nitrogen bonds is challenging due to the particularly inert and stable nature of these bonds. Here we report a formal, enantioselective one-carbon insertion into an aromatic carbon-nitrogen bond via an aromaticity dissembly-reconstruction process to directly convert anilines to chiral α-branched benzylic amines. The process involves oxidative dearomatization of para-substituted anilines, chiral sulfur ylide-mediated asymmetric aziridination, and subsequent rearrangement. Chiral sulfur ylides serve as one-carbon insertion units.
中文翻译:
通过正式的一碳插入芳族 CN 键将苯胺转化为手性苄胺。
将原子插入芳族碳氮键是合成含氮分子的一种有吸引力的方法,它具有苯胺的可用性和丰富性的优点。然而,由于这些键的特别惰性和稳定的性质,芳香碳-氮键的直接断裂具有挑战性。在这里,我们报告了一种正式的、对映选择性的单碳插入到芳香碳氮键中,通过芳香性分解重建过程将苯胺直接转化为手性 α-支化苄胺。该过程包括对位取代苯胺的氧化脱芳构化、手性硫叶立德介导的不对称氮丙啶化以及随后的重排。手性硫叶立德用作一碳插入单元。