二苯丁脂类木脂素及衍生物的合成和抗肿瘤活性研究

以胡椒醛和藜芦醛为原料, 通过Stobbe缩合和烷基化反应构建木脂素骨架、手性试剂拆分, 经官能团转换后, 得到了10个二苯丁脂类木脂素, 其中4个为天然产物. 合成得到的化合物进行了抗肿瘤活性测定, 结果表明, 部分化合物物具有较强的抑制乳腺癌细胞活性.     

一个8-O-4′新木脂素化合物的对映选择性合成

报道了一条立体选择性合成赤式8-O-4′新木脂索的新路线，以Sharpless双羟化反应构筑2个手性中心，经过几步转化，得到关键中间体6，通过Mitsunobu反应进行偶联，可以得到单一赤式的8-O-4′新木脂索化合物．通过此路线，立体选择性地合成了一个天然8-O-4′新木脂素的赤式异构体。     

丁烷衍生物类木脂素13C NMR化学位移预测

借助原子电性作用矢量(AEIV)和原子杂化状态指数(AHSI),对39种丁烷衍生物类木脂素共计854个等价C原子进行表征,并建立用于模拟该类分子13C NMR化学位移的多元线性回归方程.所得定量结构波谱关系(QSSR)模型及留一法交互检验相关系数分别为r=0.981和q=0.962.进一步用从马尾松松针中分离所得新木脂素中20个13C NMR化学位移对模型进行外部验证,预测结果与实验值较接近.表明所建模型有良好稳定性和泛化力,可对丁烷衍生物类木脂素13C NMR谱学数据准确模拟.     

肥牛木中一个新的降新木脂素

报道了肥牛木素(Ceplignan)的分离方法和结构鉴定结果.     

芳基不同型双并四氢呋喃木脂素的新合成方法

双井四氢峡哺木脂素是木脂素中结构较为复杂的一类化合物[1]．由于该类化合物在抑制磷酸二酯酶活性、抗高血压、抗氧化等方面具有显著的生理活性[2]，因此引起了药物学家和合成化学家的广泛关注[3]．但有关具有2个不同芳基的双并四氢呋喃木脂素的合成方法研究却很有限，所...     

(-)-(1R,2S)-肉豆蔻木脂素的不对称合成

报道了天然产物(-)-肉豆蔻木脂素的全合成. 以香草醛为起始原料, 经Wittig反应、LiAlH₄还原和Sharplass不对称双羟化等反应构建了苏式结构的中间体; 以焦性没食子酸为原料, 经Claisen重排反应制得另一种苯丙素片段; 2个中间体通过Mitsunobu反应, 缩合并使构型翻转, 得到赤式-(-)-肉豆蔻木脂素. 为赤式8-O-4′新木脂素的合成提供了一种新方法.     

一个8-O-4'新木脂素化合物的对映选择性合成

报道了一条立体选择性合成赤式8-O-4'新木脂素的新路线. 以Sharpless双羟化反应构筑2个手性中心, 经过几步转化, 得到关键中间体6, 通过Mitsunobu反应进行偶联, 可以得到单一赤式的8-O-4'新木脂素化合物. 通过此路线, 立体选择性地合成了一个天然8-O-4'新木脂素的赤式异构体.     

倍半木脂素threo-(±)-3,4-二香草基四氢呋喃阿魏酸酯的全合成

报道了一条合成天然产物3,4-二香草基四氢呋喃阿魏酸酯的方法.以香草醛为原料,经过两步Stobbe反应构建木脂素骨架,然后再加氢、LiAlH4还原,产物经柱层析分离后得到两个异构体meso-和threo-(±)-开环落叶松脂素;它们分别与TsCl作用,发生分子内反应得到关键的四氢呋喃木脂素中间体meso-和threo-(±)-shonanin;最后,分别与MOM保护的阿魏酸缩合得到倍半木脂素threo-(±)-3,4-二香草基四氢呋喃阿魏酸酯和衍生物erythro-(±)-3,4-二香草基四氢呋喃阿魏酸酯.合成采用汇聚法,经13步,以约8%～9%的总产率得到了目标产物.     

8-O-4′新木脂素化合物的不对称合成

报道了一种手性合成8—O—4′新木脂素的新方法，其中的关键步骤是以Sharpless不对称双羟化反应来构筑手性中心并以Mitsunobu反应立体选择性地构建8—O—4′新木脂素的骨架，最终以8步反应得到了天然降碳8—O—4′新木脂素的苏赤混合物，苏赤比为2：1．     

木脂素类化合物的全合成研究

综述了本研究小组近几年在木脂素全合成研究中取得的新进展。主要包括三部分：通过β-酮酸酯偶联反应来合成去甲二氢愈创木酸及多种其它类型木脂素;通过氧化银偶联和DDQ合环首次合成黄酮木脂素(±)-Sinaiticin;通过Sharpless不对称双羟化为关键步骤首次手性合成1,4-苯并二氧六环类新木脂素。     

Synthesis of (±) Peperomins

The total synthesis of natural antitumor agent (±) peperomin A, B and C are reported. These syntheses were started from benzophenones and diethyl succinate by Stobbe condensation. Three successive steps were employed to give the (±)-peperomins.     

Aspernigerin类似物的合成及生物活性研究

以天然产物Aspernigerin为先导,将Aspernigerin结构中的一个1,2,3,4-四氢喹啉基团以芳胺类化合物替代,设计合成了15个未见文献报道的Aspernigerin类似物,结构均经过1H NMR,IR和元素分析确证.初步生物活性测试表明,大部分目标化合物均表现出了一定的杀虫和杀菌活性,其中化合物2n在200μg/mL的浓度下对小菜蛾仍表现出100%的杀虫活性,优于先导Aspernigerin和对照药剂噻虫嗪;化合物2d,2e,2j,2k表现出对黄瓜灰霉病优于先导Aspernigerin的抑制活性.     

Facile Synthesis of 4-Oxo-4H-quinolizine-2-carboxamide Derivatives

A facile synthetic method for the construction of 2-substituted-4-oxo-4H-quinolizine-based core structure has been successfully developed. The synthesis made use of a one-pot Stobbe condensation followed by cyclization starting from the commercially available 2-pyridinecarbaldehyde. The structure of the formed 4-oxo-4H-quinolizine-2-carboxylate was fully confirmed by mass spectra, ¹H NMR and ¹³C NMR, correlation spectrography, heteronuclear multiple bond correlation, and heteronuclear single quantum coherence (HSQC) spectra. The ethyl carboxylate moiety was then further functionalized via direct aminolysis by a range of amines to afford the corresponding 4-oxo-4H-quinolizine-2-carboxamides 4a–i in moderate to good yields.     

二苯骈环辛二烯类木酚素的化学合成进展

本文从合成战略的角度概述具有多种生理活性的二苯骈环辛二烯类木酚素近年来在化学合成方面的研究进展,特别是近年来合成战略的实施和新非酚氧化偶合试剂的运用。     

Synthesis and application on parallel image storage of bisfurylfulgide

The synthesis of photochromic compounds has received a great deal of attention because of their potential application in various areas such as optical information storage[1—5], photoswitches and molecular recognition[6—8]. One of the most important researches in this field is the synthesis of a variety of photochromic fulgides to establish basic correlation between their molecular structures and photochromic properties. Since 1978, Heller[9] firstly reported the synthesis of the heterocyclic…     

Synthesis and Cytotoxicity Evaluation of Some Isoquinoline Derivatives Related to 1-Arylnaphthalene Lignans

Two series of novel compounds designed as hybrids of 1-arylnaphthalene lignans with dihydroisoquinolines or isoquinolines were synthesized and evaluated for their cytotoxicities on human tumor cell lines, such as A549, Hela, PC-3 and KB. Some of the synthetic compounds exhibited their IC50 values on selected cell lines at μmol/L scale.     

A Bio‐Inspired Total Synthesis of Tetrahydrofuran Lignans

Lignan natural products comprise a broad spectrum of biologically active secondary metabolites. Their structural diversity belies a common biosynthesis, which involves regio‐ and chemoselective oxidative coupling of propenyl phenols. Attempts to replicate this oxidative coupling have revealed significant challenges for controlling selectivity, and these challenges have thus far prevented the development of a unified biomimetic route to compounds of the lignan family. A practical solution is presented that hinges on oxidative ring opening of a diarylcyclobutane to intercept a putative biosynthetic intermediate. The effectiveness of this approach is demonstrated by the first total synthesis of tanegool in 4 steps starting from ferulic acid, as well as a concise synthesis of the prototypical furanolignan pinoresinol.     

香豆素类抗凝血药及其类似物的合成

香豆素类抗凝血药及其类似物的合成;羟基香豆素;取代苯丁烯酮;缩合;香豆素类似物