Triazole-Based Anion-Binding Catalysis for the Enantioselective Dearomatization of<i>N</i>-Heteroarenes with Phosphorus Nucleophiles
作者:Theresa Fischer、Qui-Nhi Duong、Olga García Mancheño
DOI:10.1002/chem.201605660
日期:2017.5.2
The first enantioselective synthesis of chiral heterocyclic α‐amino phosphonates by nucleophilic dearomatization of quinolines and pyridines using an anion‐binding organocatalysis approach is described. Chiral tetrakistriazoles were employed as efficient hydrogen‐bond donor catalysts by forming a chiral close ion‐pair with the in situ formed N‐acyl salts and 2,2,2‐trichlorethoxycarbonyl chloride (TrocCl)
描述了使用阴离子结合有机催化方法通过喹啉和吡啶的亲核脱芳香化反应,首次手性杂环α-氨基膦酸酯的对映选择性合成。通过与原位形成的N形成手性紧密的离子对,手性四三唑被用作有效的氢键供体催化剂。酰基盐和2,2,2-三氯乙氧基羰基氯(TrocCl)。随后用各种磷亲核试剂处理离子对,例如甲硅烷基保护的亚磷酸二烷基酯和亚磷酸三烷基酯。因此,以完全或高区域选择性获得了相应的产物,对于喹啉,最高为97:3 er,对于更具挑战性的吡啶底物,最高为89:11 er。这种方法可以快速获得取代的手性环状α-氨基膦酸酯,可以轻松地将其转化为膦酸衍生物。