(±)Isokotanin A的全合成

Isokotanin A是从曲霉属Aspergillus alliaceus的菌核分离出的联香豆素化合物。本文以3,5-二羟基甲苯为起始原料, 经氧化偶联, 选择性断裂醚键等八步反应, 首次成功地合成了(±)Isokotanin A, 总收率为12%。     

(±)-Parvistemonine A的全合成

Parvistemonine A为从对叶百部中分离得的百部生物碱.以化合物7为原料,通过路易斯酸催化的傅克及内酯化的串联反应, Vilsmeier-Haack及Julia-Kocienski烯烃化等6步反应首次完成了百部生物碱(±)-parvistemonine A的全合成工作,为parvistemonine A衍生物的合成和及其生物活性研究打下基础.     

(±)-Hypoglycin A的全合成

采用Wittig试剂与环氧氯丙烷和多聚甲醛构建亚甲基环丙烷结构单元,利用2,5-二乙氧基-3,6-二氢吡嗪引入氨基酸结构单元,通过6步反应成功实现了天然植物毒素Hypoglycin A外消旋体的全合成,总收率3.2%.中间体和Hypoglyein A的结构经1H NMR表征.对反应中的问题进行了分析和讨论.     

(±)-Cycloaltilisin 7和(±)-Poinsettifolin B的首次全合成

Cycloaltilisin 7是从桑科植物面包树(Artocarpus altilis)的芽中分离出的一种新异戊烯基黄烷酮,具有组织蛋白酶K抑制活性;Poinsettifolin B也是从桑科琉桑属植物Dorstenia poinsettifolia中分离出的一种新的香叶基查尔酮,Dorstenia poinsettifolia是原产于喀麦隆潮湿森林的草本植物,用于民间雅司病和伤口感染的治疗,对治疗皮肤病也有潜在功效.以廉价的羟苯乙酮和羟苯甲醛为原料,用简单温和的方法完成了这两种天然产物的首次全合成.所有新化合物的结构都经过HRMS,1H NMR和13C NMR的确认.     

石松科生物碱(±)-Alopecuridine和(±)-Sieboldine A的全合成

Alopecuridine和Sieboldine A是从石松科植物中分离得到的石松科生物碱,在结构特征上它们具有独特的两个相邻的季碳中心和多个稠环或桥环结构,其中后者具有重要的乙酰胆碱酯酶抑制作用     

(±)-Shegansu B,Gnetuhainin F, (±)-Maackin A与(±)-Cassigarol E的全合成

对四种天然二聚二苯乙烯类化合物Shegansu B (1), Gnetuhainin F (1a), Maackin A (2)以及Cassigarol E (3)的全合成进行了研究. 以3,5-二羟基苯甲酸(4)为起始原料, 经六步反应制得异丹叶大黄素(13)和白皮杉醇(14), 在HRP/H₂O₂酶催化氧化体系中, 13和14分别进行自身的氧化偶联得到各自的二聚产物. 首次完成了1a, (±)-2和(±)-3的全合成, 并以较文献报道为高的氧化偶联产率合成了(±)-1.     

(±)-Yaequinolone A2的简洁全合成

由廉价的邻氨基苯甲酸为起始原料经6步反应以27.8%的总产率首次合成了2-喹啉酮类生物碱(±)-yaequinolone A2,关键步骤为MOM保护的α-羟基酰胺进行的高非对映选择性分子内aldol 反应。     

(±)-Mesembrine的全合成

以3-乙氧基-2-环己烯酮羰基邻位芳基化反应与Tsuji-Trost反应的串联反应作为关键步骤来构筑季碳中心,完成了番杏科生物碱Mesembrine的全合成.从商品化原料出发经6步反应以17.8%的总收率合成得到(±)-Mesembrine.     

(±)-Galbulin和(±)-8,8′-epi-aristoligone的全合成

(±)-galbulin和(±)-8,8′-epi-aristoligone属于苯代四氢萘型木脂素类化合物,具有广泛的生物活性.以3,4-二甲氧基苯乙酸为起始原料,采用Horner-Wadsworth-Emmons反应和Friedel-Crafts反应为关键步骤,经8步得到了(±)-galbulin,并通过将(±)-galbulin苄位氧化得到(±)-8,8′-epi-aristoligone.该法操作简单,路线较短,为苯代四氢萘型木脂素化合物的合成提供了参考.     

(±) Cudraflavanone B及(±)-5-O-Methyl Cudraflavanone B的全合成研究

以2,4,6-三羟基苯乙酮和2,4-二羟基苯甲醛为起始原料, 经过异戊烯基取代、选择性保护羟基、Mitsunobu反应、Claisen重排、醛酮缩合、催化环化及去保护基等步骤, 首次完成了天然异戊烯基黄烷酮Cudraflavanone B的全合成, 同时也完成了(±)-5-O-甲基-6-(2"-异戊烯基)-7,2',4'-三羟基黄烷酮的全合成研究.     

First Total Synthesis of the (±)-Preverecynarmin

The preverecynarmin(12), (+)-(1E,3E,7E,11E)-cembra-3,7,11-tetraen-6yl acetate,was first isolated in 1990 from both Armina maculata and its prey,the pennatulacean coral Veretillum cynomorium with other there briarane diferpenoids and cembene-C((1E,3E,7E,11E)-cembra-l,3,7,11-tetraen¹. As far as we known, the bioactive test and total synthesis of ¹² have not been reported yet. Herein we wish to describe the first total synthesis of (±)-preverecynarmin (12).     

The Total Synthesis of (±)-13-Hydroxyneocembrene

(13S)-hydroxyneocembrene(18), a cembranoid which was isolated in 1988 from soft coral Sarcophyton trocheliophorum¹, has been shown to be an effective inductor of the release of labeled glucose from the lecithincholesterol liposomes and have cytostatic activities². The geometrical structure and absolute configuration of 18 have been defined to be 1S, 2E, 7E, 11E, 13S. Herein, we report the total synthesis of (±)-13hydroxyneocembrene(18).     

石松属生物碱Sieboldine A的全合成研究进展

简要介绍了石松属生物碱Sieboldine A的分离、生物活性及结构特征,综述了目前国内外对于Sieboldine A的全合成研究进展,详细论述了各个实验组在引入羟胺缩醛结构及构建cis-6/5稠环体系所采取的不同策略,并介绍了一价金催化的串联烯炔环化反应、路易斯酸催化的semipinacol重排和二碘化钐引发的自由基Pinacol偶联反应在Sieboldine A全合成中的应用。     

Total Synthesis of (−)‐Indoxamycins A and B

The concise total syntheses of (?)‐indoxamycins A and B is reported. The chemistry features a seven‐step preparation of a highly congested [5.5.6] tricyclic advanced common intermediate from a readily available R‐carvone derivative. Key steps involve a Pauson–Khand reaction for the rapid construction of a basic scaffold bearing a quaternary carbon, a copper‐catalyzed Michael addition for the introduction of another adjacent all‐carbon quaternary stereocenter, and a tandem retro‐oxa‐Michael addition/1,2‐addition/oxa‐Michael addition for the installation of a trisubstituted olefin side chain. This synthetic strategy allows for easy access to both enantiomers of this family of natural products and their analogues from cost‐effective starting material through straightforward chemical transformations.     

Asymmetric Total Synthesis of (−)‐Cladospolide B

An enantioselective total synthesis of (?)‐cladospolide B was described. The key steps in this synthesis include(a) a Sharpless asymmetric dihydroxylation to elaborate syn diol at C‐4 and C‐5 positions; (b) a Mitsunobu esterification to reverse the configuration at C‐11 from (S) to (R); and (c) a ring‐closing metathesis to access the 12‐membered macrocyclic ring.