天然产物(±)-Aiphanol的全合成研究  

Total Synthesis of Natural Product(±)-Aiphanol

作　　者：王小龙[1] 夏亚穆[1] 冯建鹏[1] 曹小平[1] 潘鑫复[1] 

机构地区：[1]兰州大学化学化工学院功能有机分子化学国家重点实验室,兰州730000

出　　处：《高等学校化学学报》2005年第2期259-263,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学群体基金(批准号:20021001);国家自然科学基金(批准号:20172023)资助

摘　　要：以醛 1和 5为起始原料 ,经几步反应后用 Ag2 O偶联 ,得到含苯并二氧六环骨架的化合物 7,化合物 7经过选择性保护酚羟基 ,再用 Na IO4 / Os O4 (cat.)氧化断裂双键 ,得到关键中间体 9,化合物 9和 1 0经过Wittig-Horner反应 ,并用苯硫酚和 AIBN实现了顺式双键向反式的转化 ,脱去保护基后完成了具有新颖结构的天然产物 (± ) -Aiphanol(1 2 )的合成 .A concise synthesis procedure for the total synthesis of natural product(±)-Aiphanol 12, a novel stilbenolignan having a stilbene-phenylpropane unit with a dioxane moiety, was achieved by using simple aldehydes as the starting materials. The key steps were oxidative coupling of coniferyl alcohol 4 with catechol 6 using Ag_2O as the catalyst to give the 1,4-benzodioxane intermediate 7, followed by a selective protection of the phenolic hydroxy group of 7 to afford 8, which was oxidized by NaIO_4/OsO_4(cat.) to give the key intermediate aldehyde 9. Then after Wittig-Horner reaction followed by conversion of Z-isomer to E-isomer using thiophenol in refluxing benzene in the presence of azoisobutyronitrile(AIBN) to produce 11, which underwent deprotection with diluted HCl in methanol to afford the titled compound(±)-Aiphanol 12 conveniently.{

关 键 词：(±)-Aiphanol 二苯乙烯 苯并二氧六环 Ag_(2)O偶联 NaIO_(4)/OsO_(4)(cat.)氧化 

分 类 号：O625[理学—有机化学]