串联反应一锅合成2-酯基多环稠合1,5-苯并硫氮杂[艹卓]化合物

Synthesis of 2-ester Polycyclic Fused 1,5-benzothiazepines via One-pot Tandem Reactions

以取代的邻氨基苯硫酚、取代的1-茚酮、乙醛酸乙酯为原料,乙醇为溶剂,三氯化铈作催化剂,三组分串联一锅合成了10种2-酯基多环稠合1,5-苯并硫氮杂[艹卓]化合物.首先,取代的1-茚酮与乙醛酸乙酯经Knoevenagel反应制得α,β-不饱和酯类化合物,不分离中间体,再与邻氨基苯硫酚上亲核性的巯基发生共轭加成,生成氨基酮中间体,其另一亲核性的氨基进攻羰基发生分子内亲核加成、脱水环合成亚胺或烯胺结构的多环稠合1,5-苯并硫氮杂[艹卓]化合物.该合成方法摒弃了传统的多步反应,具有原子经济、操作简便、反应条件温和、产率较高、选择性好且绿色环保的优点.

In this paper,ten novel 2-ester polycyclic fused 1,5-benzothiazepine compounds were obtained via one-pot three-component tandem reactions with CeCl_(3) as catalyst in ethanol.These reactions were achieved by reacting substituted o-aminothiophenol,substituted 1indanone,ethyl glyoxylate.The reaction process was the Knoevenagel reaction between substituted 1-indanone and ethyl glyoxylate to requireα,β-unsaturated ester compounds without separating intermediates.the aminoketone intermediate was formed by the conjugate addition of the nucleophilic sulfhydryl group on o-aminothiophenol.Then,the polycyclic fused 1,5-benzothiazepine compounds of imine or enamine structure were formed by intramolecular nucleophilic addition and dehydration cyclization that another nucleophilic amino group attacks the carbonyl group.The synthesis method abandons the traditional multi-step reaction and has the advantages of atomic economy,simple operation,mild reaction conditions,high yield,good selectivity and environmental protection,respectively.