利用改进的Pictet-Spengler反应合成多取代β-咔啉  

Synthesis of Polysubstitutedβ-Carboline via Improved Pictet-Sengler Reaction

作　　者：钟铮[1] 张京玉[1] 密霞 杨怀霞[1] ZHONG Zheng;ZHANG Jingyu;MI Xia;YANG Huaixia(School of Pharmacy,Henan University of Chinese Medicine,Zhengzhou 450046,China)

机构地区：[1]河南中医药大学药学院,河南郑州450046

出　　处：《合成化学》2023年第10期793-797,共5页Chinese Journal of Synthetic Chemistry

基　　金：河南中医药大学科研苗圃工程资助项目(MP2022-136)。

摘　　要：β-咔啉结构广泛存在于生物活性分子之中,为探索非酸性反应条件下合成β-咔啉衍生物的方法,以色胺类化合物和醛类为原料,以改进的Pictet-Spengler反应为关键步骤,再经氧化脱氢合成4个多取代β-咔啉化合物(2a~2d),其结构经1 H NMR和MS(ESI)确证。经过对Pictet-Spengler反应步骤中物料比、溶剂、反应温度与时间进行考察后发现:在色胺类化合物为2.0 mmol,醛为3.0 mmol,六氟异丙醇钙为0.4 mmol,二氯甲烷为20.0 mL,室温反应24 h的最优条件下,四氢-β-咔啉化合物中间体(1a~1d)的收率为75%~89%,反应存在取代基效应,含芳香性基团底物收率较高。β-carboline structure was widespread found in bioactive molecules,for investigating the preparation ofβ-carbolines under non-acid reaction condition,four polysubstitutedβ-carbolines(2a~2d)were synthesized by the improved Pictet-Spengler as key step and followed oxidized dehydrogenation from tryptamines and aldehydes,which were confirmed by 1 H NMR and MS(ESI).As to the improved Pictet-Spengler reaction,conditions such as substrates ratio,solvent,reaction temperature and time were investigated.Under the optimized conditions[tryptamines 2.0 mmol,aldehydes 3.0 mmol,calcium bis-hexafluoroisopropoxide 0.4 mmol,dichloromethane 20.0 mL,reacted at rt for 24 h,the obtained yields of precursors tetrahydro-β-carbolines(1a~1d)were 75%~89%respectively.It was found that substrates burdened aryl groups lead to higher yield.

关 键 词：β-咔啉 Pictet-Spengler反应 色胺 六氟异丙醇钙 四氢-β-咔啉 氧化脱氢反应 2 3-二氯-5 6-二氰对苯醌(DDQ) 

分 类 号：O625[理学—有机化学] O621.3[理学—化学]