Spirotryprostatin类生物碱的合成研究进展

Spirotryprostatin类生物碱是一类具有螺环吲哚二酮哌嗪结构的生物碱,其结构特点是吲哚部分和二酮哌嗪部分通过一个螺碳原子手性中心相连.由于具有这样特殊的结构使得螺环吲哚二酮哌嗪化合物具有一些生理和药理活性,尤其对细胞周期有较好的抑制活性.近年来,spirotryprostatin类生物碱的合成得到了广泛的研究,根据其结构中螺环手性中心形成的方法不同,对spirotryprostatin类生物碱的全合成研究进展进行综述.     

3,4-桥环吲哚类生物碱的合成进展

3,4-桥环吲哚类生物碱是吲哚类生物碱中非常重要的一类分子,由于独特的结构和良好的生物活性,其合成吸引了有机合成化学家的广泛兴趣.以3,4-桥环构筑位点作为分类方式概述了近年来该类天然产物的合成进展.     

无过渡金属催化条件下合成3,3'-二吲哚甲烷衍生物的最新进展（英文）

3,3'-二吲哚甲烷类化合物是一类重要的吲哚生物碱,其结构单元广泛存在于天然产物、功能性材料以及合成药物分子中.因其具有多样的生物活性和功能,如抗氧化、抗炎症、抗血管生成、抗菌以及抗癌活性等,构筑3,3'-二吲哚甲烷类杂环化合物备受关注.传统的合成方法,尤其是对称结构的3,3'-二吲哚甲烷类化合物的合成主要在化学量的Br?nsted酸或Lewis酸存在下,吲哚衍生物与羰基化合物经傅-克反应缩合得到.而过渡金属的使用可引起化合物中金属残留以及环境污染.总结和探讨了从2010年至今3,3'-二吲哚甲烷类化合物的合成方法,尤其是对无过渡金属参与条件下,对称结构的3,3'-二吲哚甲烷类化合物以及非对称结构3,3'-二吲哚甲烷类化合物制备的最新进展以及相应的反应机理,旨在为该类化合物生物活性测试提供重要的理论依据和技术支持.     

合成双吲哚甲烷类衍生物的研究进展

双吲哚甲烷类衍生物具有丰富的生物活性和药理活性,在医药领域得到了广泛的应用.近年来,对双吲哚甲烷类衍生物的合成研究引起了人们的热点关注.对双吲哚甲烷类衍生物的合成方法进行了综述,并将催化剂按照不同的类型分为:(1)路易斯酸催化剂,(2)分子碘催化剂,(3)质子酸催化剂,(4)固载催化剂,(5)杂多酸催化剂,(6)有机小分子催化剂,(7)配合物催化剂,(8)离子液体催化剂,(9)其它类型的催化剂.     

新型海洋双吲哚类生物碱的研究进展

双吲哚类生物碱是近年来分离到的一类很重要的海洋天然产物。由于这类化合物具有新颖的化学结构和多种生理活性,因此它们引起了科学家极大的兴趣。本文综述了近年来新型海洋双吲哚类生物碱的研究进展。     

3-取代吲哚衍生物的合成*

目前吲哚化学的研究是杂环化学中最活跃的领域之一,特别是3-取代吲哚衍生物,已用于许多天然产物和相应具有生物活性化合物重要骨架的构筑,其合成方法的研究格外令人注目。近年来,由吲哚一步合成3-取代吲哚衍生物的报道剧增。本文按合成过程中所用催化剂的种类,综述近几年来由吲哚为原料一步合成二吲哚甲烷、β-吲哚酮、β-吲哚醇、β-吲哚硝基化合物和α-吲哚甲胺等为代表3-取代吲哚衍生物的研究进展。     

对映纯吲(口朶)喹嗪的合成

3-乙酰基-1,4,6,7,12,12b-六氢吲哚[2,3-a]喹嗪(15,16)是吲哚生物碱及羟吲哚生物全合成中用途极广的通用建筑块。合成对映纯的15和16,一直是吲哚生物碱及羟吲哚生物碱全合成中的重要课题。Winterfeldt 首先报道了外消旋体15/16的合成及它与丙二酸二甲酯的高度立体选择性加成。为了改进阿马里新的全合成,Mandal 等1985年再次研究了     

诱导效应指数用于吲哚类生物碱质谱特征预测

在原有质谱裂解理论的基础上, 结合诱导效应指数, 通过比较吲哚生物碱中两类不同化学环境中的氮原子(吲哚环上的氮原子Na和侧链上的氮原子Nb)周围取代基诱导效应指数, 对质谱碰撞过程中电荷定域及吲哚生物碱的质谱特征进行了预测, 结果与标准物质质谱数据完全相同. 建立了利用比较杂原子诱导指数从化合物结构直接预测吲哚生物碱质谱特征的新方法. 该方法可用于吲哚生物碱和其它含氮化合物及其代谢产物的质谱特征的预测.     

3,4-桥环吲哚类生物碱的合成研究进展

取代的吲哚类天然产物是自然界中普遍存在的一类杂环化合物,由于其具有广泛的生理活性,以及相当一部分作为重要的临床使用药物,100多年以来,吲哚的合成及官能团化一直是有机合成化学家关注的一个重要领域.在众多吲哚类生物碱中,含有3,4-桥环吲哚骨架的天然产物占据了相当一部分,由于其独特的结构和良好的生物活性,这些分子引起了有机合成化学家的广泛兴趣.重点概述了构建3,4-桥环骨架的主要合成方法和策略,并对一些方法在天然产物全合成中的应用作简要介绍.     

磷酸催化的3-芳基吲哚酮与联烯酰胺的加成反应

3’3-二取代吲哚酮类化合物是一类重要的有机合成中间体,是许多天然生物碱或者药物的结构母核,该类化合物的合成是为近十几年研究的热点之一。3-取代吲哚酮的直接官能化是合成3’3-二取代吲哚酮类化合物常用的方法之一,以3-芳基吲哚酮与联烯酰胺为底物,磷酸为催化剂,室温条件下,通过一步加成反应得3’3-二取代吲哚酮类化合物,收率60%~70%,该反应的原料廉价易得,反应条件温和,经济高效,符合原子经济学的理念。      

单萜吲哚生物碱Uleine及其衍生物的合成进展

生物碱uleine及其衍生物从结构上看属于单萜吲哚生物碱,它们共同的结构特征是吲哚核与碱性氮原子之间只有一个碳相隔,而不像其它单萜吲哚生物碱有两个碳原子.由于其结构特异,天然含量少,因而其合成工作一直吸引着化学工作者.总结uleine生物碱及其衍生物的合成方法,根据构建环的种类不同,把合成方法分为五类.大部分方法都是以吲哚和吡啶衍生物为起始原料进行四环的合成,有几条合成路线简短易行.     

Enantioselective synthesis of alkaloids from phenylglycinol-derived lactams

This review is focused on recent synthetic achievements and ongoing work in our laboratory using phenylglycinol-derived oxazolopiperidone lactams as starting materials for the enantioselective synthesis of piperidine-containing alkaloids: madangamines, 2,5-disubstituted decahydroquinoline and 1-substituted tetrahydroisoquinoline alkaloids, the indole alkaloids 20S- and 20R-dihydrocleavamine and quebrachamine, and indole alkaloids of the uleine and silicine groups.     

Indole diterpenoid synthetic studies. Construction of the heptacyclic core of (-)-nodulisporic acid D

[structure: see text] Construction of the heptacyclic core of (-)-nodulisporic acid D, a representative member of a recently discovered class of architecturally complex, ectoparasiticidal indole alkaloids, has been achieved. The modular synthetic strategy comprises an expedient, stereocontrolled synthesis of a tricyclic western hemisphere, in conjunction with union of an eastern hemisphere, exploiting the 2-substituted indole synthetic protocol introduced and developed in our laboratory.     

An efficient approach to Aspidosperma alkaloids via [4 + 2] cycloadditions of aminosiloxydienes: stereocontrolled total synthesis of (+/-)-tabersonine. Gram-scale catalytic asymmetric syntheses of (+)-tabersonine and (+)-16-methoxytabersonine. Asymmetric syntheses of (+)-aspidospermidine and (-)-quebrachamine

Described is a concise, highly stereocontrolled strategy to the Aspidosperma family of indole alkaloids, one that is readily adapted to the asymmetric synthesis of these compounds. The strategy is demonstrated by the total synthesis of (+/-)-tabersonine (rac-1), proceeding through a 12-step sequence. The basis for this approach was provided by a highly regio- and stereoselective [4 + 2] cycloaddition of 2-ethylacrolein with 1-amino-3-siloxydiene developed in our laboratory. Subsequent elaboration of the initial adduct into the hexahydroquinoline DE ring system was accomplished efficiently by a ring-closing olefin metathesis reaction. A novel ortho nitrophenylation of an enol silyl ether with (o-nitrophenyl)phenyliodonium fluoride was developed to achieve an efficient, regioselective introduction of the requisite indole moiety. The final high-yielding conversion of the ABDE tetracycle into pentacyclic target rac-1 relied on intramolecular indole alkylation and regioselective C-carbomethoxylation. Our approach differs strategically from previous routes and contains built-in flexibility necessary to access many other members of the Aspidosperma family of indole alkaloids. The versatility of the synthetic strategy was illustrated through the asymmetric syntheses of the following Aspidosperma alkaloids: (+)-aspidospermidine, (-)-quebrachamine, (-)-dehydroquebrachamine, (+)-tabersonine, and (+)-16-methoxytabersonine. Of these, (+)-tabersonine and (+)-16-methoxytabersonine were synthesized in greater than 1-g quantities and in enantiomerically enriched form ( approximately 95% ee). The pivotal asymmetry-introducing step was a catalyzed enantioselective Diels-Alder reaction, which proceeded to afford the cycloadducts in up to 95% ee. Significantly, the synthetic sequence was easy to execute and required only four purifications over the 12-step synthetic route.     

Total Synthesis of Aspidosperma and Strychnos Alkaloids through Indole Dearomatization

Monoterpenoid indole alkaloids are the major class of tryptamine-derived alkaloids found in nature. Together with their structural complexity, this has attracted great interest from synthetic organic chemists. In this Review, the syntheses of Aspidosperma and Strychnos alkaloids through dearomatization of indoles are discussed.     

Total syntheses of brominated marine sponge alkaloids

Total syntheses of six brominated marine sponge bis(indole) alkaloids of the hamacanthin, spongotine, and topsentin classes are described. Retrosynthetic analysis shows that their structures all include the 1-(6'-bromoindol-3'-yl)-1,2-diaminoethane unit 13a. This key moiety has been prepared from brominated indolic N-hydroxylamine 5b via synthetic intermediate 8b.     

A new synthetic entry to pentacyclic Strychnos indole alkaloids

Cyclization of the thionium ion generated by DMTSF treatment of dithioacetal 15 constitutes a new synthetic entry to the pentacyclic ring system of Strychnos indole alkaloids.     

Synthesis of Aristotelia-Type Alkaloids. Part XIII. Total syntheses of (+)-makonine, (+)-aristotelinone,and (+)-11,12-didehydroaristoteline

The oxidative transformation of synthetic (+)-aristoteline ((+)- 6 ) into other metabolites which had been isolated from Aristotelia species was investigated. Thus, treatment of (+)- 6 with I₂ as the single oxidant furnished the naturally occurring indole alkaloids (+)-makonine ((+)- 9 ),(+)-aristotelinone ((+)- 11 ), or (+)-11, 12-didehydroaristoteline ((+)- 7 ) in good yields, the selectivity of the oxidation process depending on the chosen reaction conditions.     

Dimeric indole alkaloids of a new type a synthetic approach to the ervafoline series

A synthetic approach towards the dimeric ervafoline indole alkaloids has been achieved $\text{via}$ a route inspired from a biogenetic hypothesis.     

Total Synthesis of (−)‐Alstofolinine A through a Furan Oxidation/Rearrangement and Indole Nucleophilic Cyclization Cascade

A reaction cascade of aza‐Achmatowicz rearrangement followed by indole nucleophilic cyclization was developed to generate the common indole‐fused azabicyclo[3.3.1]nonane core of the macroline family alkaloids. The key to the success of the strategy relies on the careful manipulation of protecting groups and judicious selection of chemoselective furan oxidation conditions. The synthetic utility was further demonstrated on the asymmetric total synthesis of (?)‐alstofolinine A.