School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
Angew Chem Int Ed Engl. 2023 Mar 27;62(14):e202216758. doi: 10.1002/anie.202216758. Epub 2023 Feb 23.
A practical, transition metal-free method allows the enantioselective synthesis of α,α-diarylmethylamines by asymmetric α-arylation of benzylamines. Enantioselective lithiation of N'-aryl-N-benzyl-N-isopropyl ureas using a chiral lithium amide base generates a benzyllithium that undergoes an unactivated stereospecific intramolecular nucleophilic aromatic substitution to generate an α,α-diarylmethylamine in the form of its urea derivative, in up to >99 % ee. Treatment with acid induces an "azatropic shift" with retention of configuration, the product of which may be hydrolysed to the target amine.
一种实用的、无过渡金属的方法允许通过不对称的芳基化反应来合成α，α-二芳基甲基胺。通过手性锂酰胺碱对 N'-芳基-N-苄基-N-异丙基脲进行对映选择性锂化，生成苯甲基锂，它经历非活化的立体专一性分子内亲核芳香取代，以脲衍生物的形式生成α，α-二芳基甲基胺，对映体过量高达>99%。用酸处理会诱导构型保持的“氮杂迁移”，其产物可以水解得到目标胺。
