氧杂环丁烷的合成

氧杂环丁烷作为一类饱和四元环醚类化合物,不仅是重要的有机合成中间体,也是天然和合成的具有抗癌、抗HIV、抑制谷氨酰胺合成酶等多种生物或药物活性化合物分子结构中的重要活性单元.因此,发展氧杂环丁烷骨架的有效合成方法非常重要.本文以分子内形成C—C键的环化反应、分子内形成C—O键的Williamson醚化反应、烯烃和醛酮[...     

两种氮杂环丁烷类药物中间体的合成

1-二苯甲基-3-羟基氮杂环丁烷(1)经过对甲苯磺酰氯取代、叠氮化及还原反应合成了药物中间体--1-二苯甲基-3-氨基氮杂环丁烷(4);1经过氧化、氰基化与还原反应合成了1-二苯甲基-3-羟基-3-氨甲基氮杂环丁烷(8).4和8的结构经1H NMR表征.     

氮杂环丁烷衍生物的合成及其抗肿瘤活性

以3-羟基氮杂环丁烷盐酸盐为原料,经取代、官能团转化制得3-氨基氮杂环丁烷化合物（3）; 3经衍生化合成了10个3-氨基氮杂环丁烷衍生物(4a~4j),其中4f~4j为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF)表征。采用MTT法初步测试了化合物的体外抗肿瘤活性。结果表明：4h对A549表现出较强的细胞毒活性（IC₅₀=8.06 μmol·L^-1）。     

3-羟甲基氮杂环丁烷盐酸盐的实用合成方法

氮杂环丁烷类化合物是一类重要的饱和四元含氮杂环化合物,在药物研发中有着广泛的应用。本文以二苯甲胺和环氧氯丙烷为起始原料,在碱性条件下反应关环构建N-杂环丁烷母核,之后依次发生羟基的氧化、Wittig反应生成环外双键,随后采用硼氢化氧化反应将双键转化为羟甲基,最后氢化脱去二苯甲基得到目标产物3-羟甲基氮杂环丁烷,反应的5步转化总收率为40%。该合成方法操作简单,原料廉价易得,避免了剧毒试剂的使用,具有很好的工业化前景。     

1,3,3-三硝基氮杂环丁烷合成研究的现状与进展

叙述近年来国外对新的高能量密度材料１，３，３－三硝基氮杂环丁烷合成研究的情况与进展，介绍了六种新的合成路线并进行了评论。     

新型3-氨基氮杂环丁烷衍生物的合成

以3-羟基氮杂环丁烷盐酸盐为原料,与4-氟苯乙酮反应制得1-（4-乙酰苯基）-3-羟基氮杂环丁烷（1）; 1经甲磺酰化反应、取代反应、还原反应及酰化反应,合成了6个新型的3-氨基氮杂环丁烷衍生物,其结构经¹H NMR和¹³C NMR表征。     

氧杂环丁烷的扩环反应

氧杂环丁烷是一类重要的小杂环化合物,也是重要有机合成中间体,在有机化学、药物化学和高分子化学中都有广泛的应用.作为具有较大环张力的小杂环化合物,氧杂环丁烷类化合物除可以发生开环反应外,也很容易发生扩环反应,构建含氧普通环到大环化合物.主要总结了氧杂环丁烷的扩环反应,包括重氮化合物作为卡宾前体与氧杂环丁烷的扩环反应、金属...     

手性氮杂环丁烷的合成及其在不对称催化反应中的应用

综述了手性氮杂环丁烷衍生物的合成方法以及它们在不对称硼氢化反应、二乙基锌对醛的加成反应、Henry反应、Diels-Alder反应和环丙烷化反应中的应用研究进展.     

N-乙酰基-3,3-二硝基氮杂环丁烷的合成

多硝基氮杂环丁烷及其衍生物因其四元杂环所具有很高的环张力能,赋予这类化合物优良的爆轰性能,从而成为一类重要的高能量密度材料,其中1,3,3-三硝基氮杂环丁烷(TNAZ)成为最具有应用前景的含能材料之一。N-乙酰基-3,3-二硝基氮杂环丁烷(ADNAZ),为白色或无色晶体,可溶于丙酮,二氯甲烷等有机溶剂。     

1,3,3-三硝基氮杂环丁烷的合成

1,3,3-三硝基氮杂环丁烷（TNAZ）作为高能量密度材料，其合成和应用研究受 到了广泛重视。本文用硝基甲烷、多聚甲醛、叔丁胺等作为起始原料，经过五步反 应合成出了TNAZ，总收率为34%，用红外光谱、核磁共振氢谱及碳谱和质谱等对其 及中间体结构进行了表征。大部分反应使用水作为反应介质，降低了合成成本，污 染明显减少。讨论了反应条件和影响反应产物收率的主要因素，获得了制备TNAZ合 适条件。     

Synthesis of 2-Oxazolines from Ring Opening Isomerization of 3-Amido-2-Phenyl Azetidines

Chiral 2-oxazolines are valuable building blocks and famous ligands for asymmetric catalysis. The most common synthesis involves the reaction of an amino alcohol with a carboxylic acid. In this paper, an efficient synthesis of 2-oxazolines has been achieved via the stereospecific isomerization of 3-amido-2-phenyl azetidines. The reactions were studied in the presence of both Brønsted and Lewis acids, and Cu(OTf)₂ was found to be the most effective.     

Total Synthesis of Talatisamine

Talatisamine ( 1 ) is a member of the C₁₉‐diterpenoid alkaloid family, and exhibits K⁺ channel inhibitory and antiarrhythmic activities. The formidable synthetic challenge that 1 presents is due to its highly oxidized and intricately fused hexacyclic 6/7/5/6/6/5‐membered‐ring structure (ABCDEF‐ring) with 12 contiguous stereocenters. Here we report an efficient synthetic route to 1 by the assembly of two structurally simple fragments, chiral 6/6‐membered AE‐ring 7 and aromatic 6‐membered D‐ring 6 . AE‐ring 7 was constructed from 2‐cyclohexenone ( 8 ) through fusing an N‐ethylpiperidine ring by a double Mannich reaction. After coupling 6 with 7 , an oxidative dearomatization/Diels–Alder reaction sequence generated fused pentacycle 4 b . The newly formed 6/6‐membered ring system was then stereospecifically reorganized into the 7/5‐membered BC‐ring of 3 via a Wagner–Meerwein rearrangement. Finally, Hg(OAc)₂ induced an oxidative aza‐Prins cyclization of 2 , thereby forging the remaining 5‐membered F‐ring. The total synthesis of 1 was thus accomplished by optimizing and orchestrating 33 transformations from 8 .     

天然产物合成中八元碳环的构建

总结归纳了近年来天然产物合成中八元碳环构建的主要方法:环合反应、裂解反应以及涉及环扩张/收缩的重排反应。     

Useful dual Diels-Alder behavior of 2-azetidinone-tethered aryl imines as azadienophiles or azadienes: a beta-lactam-based stereocontrolled access to optically pure highly functionalized indolizidine systems

Imines derived from 4-oxoazetidine-2-carbaldehydes have been found to be versatile Diels-Alder reagents in that they exhibit two reactivity patterns. 2-Azetidinone-tethered imines undergo diastereoselective reaction with Danishefsky's diene in the presence of different Lewis acids. The effect of the amount of catalyst on the conversion rate as well as on the product ratio has been studied. Under standard reaction conditions, indium(III) chloride and zinc(II) iodide provided the best yields, and indium(III) triflate the highest diastereoselectivity in the Lewis acid promoted aza-Diels-Alder cycloaddition. Treatment of the aforementioned imines with cyclopentadiene, 2,3-dimethyl-1,3-butadiene or 3,4-dihydro-2 H-pyran led to cycloadducts arising from inverse electron-demand condensation involving the beta-lactam-tethered aryl imine as the heterodiene component. In addition, the first methodology for preparing indolizidines from beta-lactams has been developed. This process involves amide bond cleavage of the beta-lactam ring in the aza-Diels-Alder cycloadducts with concomitant cyclization. Full chirality transfer occurs when the reaction is performed with an enantiomerically pure substrate.     

Fischer吲哚合成法的研究进展

吲哚及其衍生物具有某些生物活性, 其合成方法很多. 其中Fischer吲哚合成是最便捷和经济的合成方法, 应用最多. 对此法近十年来的合成工艺进行了综述和评价.     

Diversity‐Oriented Enantioselective Synthesis of Highly Functionalized Cyclic and Bicyclic Alcohols

The copper‐catalyzed hetero‐allylic asymmetric alkylation (h‐AAA) of functionalized Grignard reagents that contain alkene or alkyne moieties has been achieved with excellent regio‐ and enantioselectivity. The corresponding alkylation products were further transformed into a variety of highly functionalized cyclic and bicyclic alcohols with excellent control over the chemo‐, regio‐, and stereoselectivity.     

脱氧莪术二酮的合成

( )-莪术二酮(1)是从中药中分离出并具有明显抗癌活性的十员环倍半萜。最近,我们简要报道了(-)-莪术二酮的全合成。在全合成探索中,为了试验以 Oxy—Cope 重排反应