(24S)-2α,3α,22R,23R-四羟基-B-高-6-氮杂-5α-豆甾-7-酮的合成及活性研究  

Synthesis and bioactivity of(24 S)-2α,3α,22R,23R-tetrahydroxy-B-homo-6-aza-5α-stigmasta-7-one

作　　者：万玮 丁文艳 陈庆港 顾家 黄建平[1] 黄长干[1] WAN Wei;DING Wen-yan;CHEN Qing-gang;GU Jia;HUANG Jian-ping;HUANG Chang-gan(College of Chemistry and Materials,Jiangxi Agricultural University,Nanchang Key Laboratory of Chemical Utilization of Plant Resources,Nanchang 330045,China)

机构地区：[1]江西农业大学化学与材料学院,南昌市植物资源化学利用重点实验室,江西南昌330045

出　　处：《化学研究与应用》2023年第5期1170-1176,共7页Chemical Research and Application

基　　金：28-高芸苔素内酯的合成研究及其中试生产项目(911013470029)资助。

摘　　要：探讨28-高芸苔素内酯中内酰胺类似物的合成及植物生长调节活性,分析其构效关系。以豆甾醇为原料经甲基磺酰化、重排、羟基氧化、质子迁移、肟化、Beckmann重排、Sharpless不对称羟基化七步反应合成了(24 S)-2α,3α,22R,23R-四羟基-B-高-6-氮杂-5α-豆甾-7-酮(8a)和(24 S)-2α,3α,22S,23S-四羟基-B-高-6-氮杂-5α-豆甾-7-酮(8b),总收率为28.2%。通过FT-IR和NMR确认结构,以28-高芸苔素内酯作阳性对照,进行大豆上胚轴伸长实验。结果表明,化合物8a仅有28-高芸苔素内酯30%的活性,化合物8b效果较差,由此可知芸苔素内酯类化合物中的C-22,C-23构型和B环内酯结构对生物活性的影响非常重要。To investigate the synthesis,plant growth regulating activity and structure-activity relationship of lactam analogues in 28-homobrassinolide,(24 S)-2α,3α,22R,23R-tetrahydroxy-B-homo-6-aza-5α-Stigmasta-7-one(8a)and(24 S)-2α,3α,22S,23S-tetrahydroxy-B-homo-6-aza-5α-Stigmasta-7-one(8b)were synthesized from stigmasterol by mesylation,rearrangement,hydroxylation,proton transfer,oximation,Beckmann rearrangement and Sharpless asymmetric hydroxylation in seven steps,with an overall yield of 28.2%.The target compound was characterized by FT-IR and NMR to confirm its structure,and the soybean epicotyl elongation experiment was conducted with 28-homobrassinolide as positive control.The results indicated compound 8a had only 30%bioactivity of 28-homobrassinolide,while compound 8b was poor.Therefore,the C-22,C-23 configurations and B-ring lactone structures in brassinolides were very important for their bioactivity.

关 键 词：28-高芸苔素内酯 内酰胺 大豆上胚轴伸长实验 

分 类 号：O629.2[理学—有机化学]