紫草素的全合成研究进展

综述了天然产物紫草素的全合成研究进展, 分析了紫草素的合成路线, 讨论了各合成方法的优缺点.     

苯丙素苷Acteoside,Isoacteoside和Ligupurpuroside J的全合成

发展了一条合成苯丙素苷类化合物的通用路线,并依据此路线完成了苯丙素苷毛蕊花糖苷(Acteoside)和异毛蕊花糖苷(Isoacteoside)的全合成及紫茎女贞苷J(Ligupurpuroside J)的首次全合成.其中的关键步骤是应用金(Ⅰ)催化的鼠李糖邻炔基苯甲酸酯给体与多羟基裸露的2-苯乙基葡萄糖苷进行区域选择性糖苷化反应,成功构建天然苯丙素苷中常见的α-(1→3)糖苷键.该合成路线减少了保护基的使用,简洁高效.     

生源启发下的喜树碱的简洁形式合成

以色胺和方便易得的乙基戊烯二醛盐为起始物,以简洁的步骤(最终实现喜树碱全合成共9步反应)完成了喜树碱的生源启发下的无保护基形式合成.合成路线涉及关键的Pictet-Spengler反应,分子内氧杂Diels-Alder反应高效构建单萜吲哚中间体,以及Winterfeldt高效仿生氧化吲哚合成喹啉酮结构.     

全合成先锋霉素的重要中间体—噻嗪酸酯的研究

近年来对于先锋霉素全合成的研究有了很大的发展.已报道的全合成路线中,以Merck-Syntex^[1]路线比较实用.为了合成先锋霉素的重要中间体——噻嗪酸酯3,Merck-Syntex使用了Wittig反应,步骤比较长.他们所以采用Wittig反应,是考虑到酯基旁边的α-H不够活泼,不能与甲基酮起缩合反应.     

灯台生物碱Strictamine的全合成

灯台生物碱具有复杂多样的结构和显著的生理活性,针对此类分子的化学合成引起了有机化学界的广泛关注。其中的代表性化合物strictamine在结构上具有笼状的methanoquinolizidine核心骨架和C7位全碳季碳手性中心,在合成上具有重要挑战。关于该化合物的全合成已有超过40年的研究历史,而直到最近两年才取得突破性的进展。本文针对2016年以来关于strictamine的三条全合成和四条形式合成路线进行简要介绍,主要剖析了各条合成路线中的关键策略和反应,并对进一步的研究进行了展望。     

抗癌药物紫杉醇的全合成-Nicolaou法全合成紫杉醇的剖析

介绍和剖析了用Nicolaou法全合成紫杉醇的方法,包括合成的战略和路线,关键反应和保护基的应用等.     

Brefeldin A全合成研究新进展

Brefeldin A(布雷菲德菌素甲)是一种天然抗生素, 最早发现于1958年, 许多种微生物中都能产生该化合物. 由于其有趣的结构和显著的抗真菌、抗病毒、抗肿瘤等生物活性, 该化合物很早就引起合成化学家们的注意. 到目前为止, 文献中有报道的全合成和表观合成已有30多种. 对近十年来的全合成及部分表观合成进行了综述, 对各路线的主要优缺点也进行了简要的分析. 一些类似物的合成也一并予以简介.     

Platencin(平板素)的全合成研究进展

Platencin是西班牙土壤样品中平板链球菌(Streptomyces platensis)MA7339的代谢产物,骨架具有6/6/6三环笼状结构,能够抑制细菌脂肪酸的生物合成,具有良好的广谱抗菌活性.综述了自2010年以来platencin的全合成以及形式合成的研究进展,对各个路线的反应步骤进行了说明,对合成策略进行了重点讨论.     

Cystothiazole A的改进全合成

本文研究了cystothiazoleA全合成的一条改进路线．在该全合成策略中,我们成功发展了一种由酰基嗯唑啉酮到β-酮酸酯的一步转化方法．通过该方法,CystothiazoleA的合成路线变得更加高效．同时该策略对于合成其它相关的β-取代-β-甲氧基丙烯酸酯也具有潜在的意义．     

洋茉莉醛中间体3,4-亚甲二氧基苯乙醇酸的合成与表征

茉莉醛又称胡椒醛,学名3,4-亚甲二氧基苯甲醛(3,4-methylenedioxy benzaldehyde),广泛应用于合成香料、医药、食品、日化、电镀等领域.目前全球洋茉莉醛生产主要集中在我国、日本、美国和欧盟,总产能约1万吨/年.我国和日本主要采用天然黄樟油路线合成洋茉莉醛.随着全球生产量的不断增大,黄樟油资源面临枯竭,研究和开发以简单化学品为原料的全合成方法成为当务之急[1][2].在酸催化下,以乙醛酸和胡椒环为原料合成3,4-亚甲二氧基苯乙醇酸,再经氧化得到洋茉莉醛的路线,具有工艺设备简单、三废少、收率高、产品纯度高等优点,成为替代黄樟油路线法较为理想的全合成路线[3][4].     

(±)-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.     

A new access to efaroxan and its 5-amino derivatives

The formal total synthesis of racemic efaroxan, a 2-disubstituted 2,3-dihydrobenzofuran having interesting therapeutic properties, and the preparation of some 5-amino derivatives were achieved using a convergent approach. The key intermediates of both syntheses were obtained after a [3+2] cycloaddition reaction between two easily accessible partners.     

The total synthesis of (±)-arisugacin A

A 20-step total synthesis of (±)-arisugacin A with an overall yield of 2.1% is described here in detail. This synthesis features a formal [3+3] cycloaddition reaction of α,β-unsaturated iminium salts with 6-aryl-4-hydroxy-2-pyrones through a highly stereoselective 6π-electron electrocyclic ring-closure of 1-oxatriene. A strategic dihydroxylation-deoxygenation protocol leading to the desired angular C12a-OH was developed to serve as a critical step in leading to the final total syntheses of arisugacin A. This synthetic endeavor also led to an interesting and unexpected retro-aldol-aldol sequence in the AB-ring.     

Thirty-five years of synthetic studies directed towards the histrionicotoxin family of alkaloids

This article brings together for the first time reviews of all the synthetic attempts towards the spirocyclic histrionicotoxin alkaloids published since the discovery of the group in 1971. This covers 5 total syntheses of the fully unsaturated parent alkaloid HTX-283A, 7 total syntheses of perhydrohistrionicotoxin, 15 total syntheses of other members of this alkaloid family, 25 formal syntheses, and 19 partial syntheses involving the successful formation of the core azaspirocyclic structure but lacking advancement towards the target structure.     

Consecutive sigmatropic rearrangements in the enantioselective total synthesis of (−)-joubertinamine and (−)-mesembrine

Joubertinamine and mesembrine are two related alkaloids isolated from Sceletium plants. From the perspective of chemical synthesis, the major challenge posed by joubertinamine and mesembrine is undoubtedly the construction of the benzylic quaternary stereogenic center. We became intrigued by the prospect of applying successive sigmatropic rearrangements to build the key structural features of these alkaloids in enantioselective manner. In this article, we detail our results in this area, which include the enantioselective total synthesis of (−)-joubertinamine and (−)-mesembrine.     

Concise syntheses of (±)-dichroanone, (±)-dichroanal B, (±)-taiwaniaquinol B, and (±)-taiwaniaquinone D

The total syntheses of dichroanone and dichroanal B, as well as the formal syntheses of taiwaniaquinol B and taiwaniaquinone D, are reported.     

Cross metathesis as a general strategy for the synthesis of prostacyclin and prostaglandin analogues

[reaction: see text] A cross metathesis (CM) approach has been successfully applied to introduce fully functionalized omega-side chain appendages of various prostacyclin and prostaglandin analogues, resulting in high (E)-selectivities for the C13-C14 double bond and leading to the total syntheses of isocarbacyclin, 15R-TIC, carbacyclin, and PGF(2)(alpha) and the formal syntheses of 15-deoxy-TIC and PGJ(2).     

Biosynthesis, total syntheses, and antitumor activity of tanshinones and their analogs as potential therapeutic agents

Tanshinones are a series of abietane diterpenes, isolated exclusively from Salvia miltiorrhiza and related species. More than 40 tanshinones and their analogs have been isolated since the 1930s. Their biosynthetic pathway correlates with the MEP/DOXP pathway, and many key enzymes, such as mCPS, are responsible for establishing their molecular scaffolds and stereospeci?city. Because of their unique structural characteristics and promising biological activities, total syntheses of various tanshinones have attracted the interest of many synthetic chemists, including R. H. Thomson, H. Kakisawa, R. L. Danheiser, Y. Inouye and J. K. Snyder. Tanshinones and their analogs exhibit interesting and broad antitumor activity in various cell and animal models. Most recently, the tanshinone analog neo-tanshinlactone has shown potent and selective activity against breast cancer. This review will discuss the biosynthesis, total syntheses, and antitumor activities of tanshinones,especially neo-tanshinlactone and its analogs.     

抗疟倍半萜过氧化物青蒿素和鹰爪素A的全合成

青蒿素和鹰爪素A是从中药中分离的两个含过氧基团的抗疟活性组分。特别是青蒿素已成为新型的抗疟药物,因而引起合成化学家的极大兴趣。现对该两个化合物的全合成作一综述。