(-)-N-芳硫基樟脑内磺酰胺的合成及其与β-酮酯的反应  

Synthesis of(-)-N-Arylthiocamphorsultams and The Reaction withβ-Ketoesters

作　　者：姜亮 陈甫雪 JIANG Liang;CHEN Fu-xue(School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China)

机构地区：[1]北京理工大学化学与化工学院,北京102488

出　　处：《合成化学》2022年第3期200-208,共9页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(21971013)。

摘　　要：(1S)-(-)-2,10-樟脑内磺酰胺与原位生成的芳基硫氯反应,制得系列亲电性N-芳硫基樟脑内磺酰胺试剂(1a~1c),并将其应用于与β-酮酯活泼氢的不对称亲电取代反应,合成了具有光学活性的α-芳硫基-β-酮酯衍生物。考察了试剂结构、底物酯基的体积及环大小、添加剂种类及用量,以及溶剂、温度等反应条件对手性诱导效率的影响。初步实验结果表明:以(1S)-(-)-N-对甲基苯硫基樟脑内磺酰胺(1a)为亲电试剂,六元环β-酮甲酯为底物,甲苯为溶剂,碳酸钾为碱,室温反应48 h,α-芳硫基-β-酮酯的收率可达91%,对映选择性达40%ee。A family of electrophilic aryl mercapto reagents(1a~1c)were synthesized by the reaction of(1S)-(-)-2,10-camphorsultam and the in situ generated arylsulfenyl chloride,which was applied to the asymmetric electrophilicα-substitution of the active proton inβ-ketoesters,giving the corresponding optically activeα-arylthio-β-ketoester derivatives.The effects of the structure of the electrophiles and substrates,the nature and amount of additives,as well as reaction parameters such as solvent and reaction temperature on the transfer efficiency of chirality were preliminarily investigated.Thus,the desired product 3a~3l were obtained in up to 91%yield and up to 40%ee using(1S)-(-)-N-(p-tolylthio)-2,10-camphorsultam(1a)as the reagent,and six-membered ringβ-ketoester as the substrate,potassium carbonate as the base,toluene as the solvent,stirring at room temperature for 48 h.

关 键 词：不对称合成 樟脑内磺酰胺 α-芳硫化反应 β-酮酯 手性诱导 条件优化 

分 类 号：O621[理学—有机化学]