手性磺酸基联萘(并冠)醚的合成及水相中直接催化三组分Mannich反应

由1,1'-联-2-萘酚经Williamson合成法及与二甘醇/三甘醇单/双对甲苯磺酸酯反应, 制得10个联萘(并冠)醚, 用氯磺酸磺化, 分别得到10个6,6'二磺酸基联萘(并冠)醚(3a～3f, 6a～6d). 将手性磺酸基联萘(并冠)醚作为Brønsted酸催化剂, 水相中直接催化苯胺、苯甲醛和环己酮三组分Mannich反应, 获得高化学收率(90%～99%)和非对映选择性产物, 其中(R)-6,6'-二磺酸基联萘并-20-冠-6的非对映选择性de 98%. 催化苯胺/取代苯胺、苯甲醛和苯乙酮的反应, 结果显示反应与催化剂和底物分子结构、反应温度及反应时间有关. 催化剂容易回收, 重复使用多次活性基本不减.

Syntheses of Chiral Sulfobinaphtho-Crown Ethers and Their Catalytic Properties for the Three-Component Mannich Reaction in Water

Ten 6,6'-disulfobinaphtho-crown ethers were synthesized via sulfonization of the corresponding crown ethers. Chiral sulfobinaphtho-crown ethers were used to catalyze the 3-component Mannich reaction of analine, benzaldehyde and cyclohexanone in aqueous media and show excellent yield and diastereoselec- tivity up to de 98%. Investigation into the reactions of analine/substituted analine, benzaldehyde and hyp- none demonstrates that the molecular structures of the catalysts and the substrate compounds, as well as the reaction temperature and time can influence the catalytic results.