“Drimane”类倍半萜及异戊烯基类黄烷酮天然产物的全合成研究.pdf

“Drimane”类倍半萜及异戊烯基类黄烷酮天然产物的全合成研究.pdf宁夏大学硕士学位论文“Drimane”类倍半萜及异戊烯基类黄烷酮天然产物的全合成研究姓名:江世智申请学位级别:硕士专业:有机化学指导教师:杨金会 20100401 摘要本论文详细介绍了“d血n觚e”类倍半萜和异戊烯基类黄烷酮天然产物的全合成研究,主要内容包括以下三个部分: 一:drimane类倍半萜的研究现状简要综述了Drimane类倍半萜化合物的结构、。二:天然产物Isodrimenedi01的不对称全合成研究以香叶基醇为起始原料,经过酯化(羟基的保护)、A咖ix—B催化的不对称双羟化反应, 环氧化、烯丙位醇羟基的溴代,烷基化、烯醇磷酸酯化合物,烯丙基硅化合物,路易斯酸催化下的分子内环化,氢化铝锂对酯基的还原等九步反应首次完成了天然产物Isodrimenediol的不对称全合成研究。所有新化合物的结构都经过‘H N躲,IR,骼确认,关键化合物的结构还经过 HRMS和¨C inmaojuesides A及 xianglinmaojuesides B的合成研究正在进行中。三:异戊烯基黄烷酮的合成研究以廉价的对羟基苯甲醛,邻羟基苯乙酮和2,4一二羟基苯乙酮为起始原料,经过C一异戊烯基化,选择性的酚羟基保护,羟醛缩合,催化环化和去保护基等步骤,首次完成了天然产物异戊烯基黄烷酮2,3_二氢-2一苯基_8一(3-甲基一丁基-2-烯基)-4H-1一苯并吡喃一4-酮,2,3一二氢-2-(4一羟苯基)-8一(3-甲基一丁基一2—烯基)-4H一卜苯并吡喃一4一酮以及AbyssinonelI的全合成研究。关键词:DrLqlanc倍半萜,糖苷衍生物,异戊烯基黄烷酮,天然产物,全合成 Abstract Thisthesisaims atthestudies on thetotalsynthesis pounds drimane sesquiterpenoids and isoprenylflavanoids,which consistsofmainly thefollowing parts: l:The firstchapter briefly l'evicwthes仃ucmm,,翱otlrce and distribute,biological activity and synthesis ofdrimane sesquitcrlgnoids. 2:The firstenantioselective synthesis of isodrimenediol was achieved in9steps from gc艇aniol, through hydroxyl protection,AD·m政巾-Catalyzed Asymmetric Dihydroxylation,epoxidafion, bromination,alkylation,pounds,anyl siliconandcyclization catalyzed by Lewis acid' Reduction ofhydroxyl ester s仃ucturcs of pounds wereconfirmedby IR, 1HNMR pounds hasalsobeen confirmed by HRMS and MR. Finally alsodiscussed the Problems and key factorinsynthesis synthesis of other drimane sesquiterpenoids xianglinmaojuesides Aandxianglinmaojuesides B under way. —。-3:Three natural isoprenylflavanoids(:1:)-8-(3-methyl-but-yl)一2-yl-chroman-4-one, (:t:)-2-(4-hydroxyphenyl)一8-(3-methyl-but-2-enyl)-chroman-4-one and Abyssinonell were synthesized through C-prenylation,sdect/ve protection of phenolic hydroxyl group,aldol condensation, cyclization and deprotection starting from cheap 4-hydroxybenzaldehyde,2-hydroxyacetophenone and 2,4-dihydroxyacetophenone wi