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综述与进展
N-苯氧基乙酰胺导向的碳氢键官能团化反应研究进展
姜晓蕾, 郝佳奇, 周国庆, 侯程程, 胡芳东
2019, 39(7): 1811-1830  doi: 10.6023/cjoc201902019
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摘要:
碳氢键活化反应因具有原子经济性和步骤简捷性的特点,近年来成为有机化学研究的热点领域之一.在传统的碳氢键活化反应中,通常需要加入等物质的量的氧化剂来实现催化剂的再生,使催化循环顺利地发生.而N-苯氧基乙酰胺作为一种新型的含有氧化型导向基的反应底物,可以有效地避免等物质的量外加氧化剂的使用,使碳氢键活化在氧化还原中性的条件下进行.综述了N-苯氧基乙酰胺在有机合成领域特别是碳氢键活化反应中的最新研究进展,并对反应的机理进行了讨论.
芳甲基叠氮化合物与烯烃及其衍生物反应研究进展
李秀英, 李亚军, 韦贤生, 罗金荣, 黄国保, 谭明雄
2019, 39(7): 1831-1836  doi: 10.6023/cjoc201903001
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芳甲基叠氮化合物(ArCH2N3)可以为有机反应提供氮源,是一种性质稳定、合成简单的试剂,在有机合成化学领域被广泛应用.综述了最近五年来芳甲基叠氮化合物与烯烃在有机合成反应中的最新研究进展.分别叙述了芳甲基叠氮化合物在有机反应中与烯烃及其衍生物的底物适应范围和反应机理,为今后芳甲基叠氮化合物与烯烃类化合物的反应在有机合成中的应用提供参考.
高价碘试剂的有机电化学合成及应用研究进展
张怀远, 唐蓉萍, 石星丽, 颉林, 伍家卫
2019, 39(7): 1837-1845  doi: 10.6023/cjoc201902006
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芳基碘化物的阳极氧化是一种绿色高效的用于合成高价碘试剂的方法,该方法用电流代替了化学试剂,避免了使用价格昂贵、反应后处理棘手的氧化剂,如m-CPBA,H2O2,Oxone,Selectfluor等.利用电化学合成的高价碘试剂,既可促进氟化、氧化环化等反应,也可成功地应用于天然产物的全合成.一价碘/三价碘氧化还原体系可用来高效地形成碳碳键、碳杂原子等化学键.此外,能回收循环再利用的芳基碘介质可用于间接阳极氟化,且容易和产物分离.总结近年来高价碘试剂的电化学合成方法及其介导的各种化学反应.
多功能荧光探针的设计、合成与应用研究进展
陈思鸿, 庞楚明, 陈孝云, 严智浩, 黄诗敏, 李香弟, 钟雅婷, 汪朝阳
2019, 39(7): 1846-1857  doi: 10.6023/cjoc201901033
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多功能荧光探针可检测多个阴阳离子、小分子等,相对于单分析的荧光探针能提高检测效率、降低分析成本,故广受关注.根据分子结构特点,将多功能荧光探针分为有机小分子型、聚合物型和金属有机配合物型等三大类,从检测对象和性能出发,重点综述了近几年国内外多功能荧光探针在分子设计、合成与检测应用等方面的新进展,并展望了多功能荧光探针的发展潜力,指出开发能够在同体系中同时识别多个分析物的探针是未来研究中的重点方向.
3D打印技术在有机合成化学中的应用
赖石林, 廖旭, 张辉, 蒋岩, 刘源岗, 王士斌, 熊兴泉
2019, 39(7): 1858-1866  doi: 10.6023/cjoc201901001
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相对于传统的材料去除-切削加工技术,3D打印作为一种“自下而上”的材料累加制造方法,不仅操作简单、制造成本更低以及可实现快速生成,而且可实现复杂结构件的精确定制.因此,3D打印已成为第三次工业革命的代表性技术.近年来,化学家们将3D打印技术与有机合成相结合,在多通道异相催化剂和新型反应装置的研发设计等方面取得了积极的进展,进而使这项技术在有机合成领域中应用越来越广泛.对近年来基于3D打印技术的有机合成研究进展进行了综述,涵盖基于3D打印异相催化剂或催化剂载体、3D打印反应装置和3D打印流反应器,并对该领域的发展趋势进行了展望.
苯丙氨酸衍生物的碳氢键直接官能化反应进展
李小芳, 熊伟康, 丁秋平
2019, 39(7): 1867-1874  doi: 10.6023/cjoc201901029
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苯丙氨酸衍生物具有显著的生物活性,被广泛应用于药物分子中.主要综述了近年来基于苯丙氨酸衍生物的碳氢键直接官能化反应,有效构建了C—I,C—C[含C(sp2)—C(sp2),C(sp2)—C(sp)和C(sp2)—C(sp3)键],C—N,C—B和C—O键,从而简洁、高效地实现了苯丙氨酸衍生物的邻位碘化及分子内胺化反应,邻位烷基化、芳基化、烯基化、炔基化、酰基化、酰氧基化、胺化和硼化反应,以及间位芳基化和烷基化反应等.
黄酮苷的合成研究进展
徐焕基, 李哲明, 吴云秋, 罗迪, 邱莉, 谢集照, 李雪华
2019, 39(7): 1875-1890  doi: 10.6023/cjoc201811002
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黄酮苷广泛存在于自然界植物,具有广泛的药理活性和潜在的药用价值,其合成方法值得研究,对2014年至2018年黄酮苷的合成进行综述.黄酮苷的合成主要包括化学合成和生物合成两大类,而化学合成又分为全合成和半合成,其中全合成主要有β-丙二酮酸化关环法(Baker-Venkataraman,BK-VK法)和查尔酮氧化关环法(Algar-Flynn-Oyamada,AFO法)两种经典方法;半合成是以芦丁、槲皮素、山萘酚、柚皮素等天然黄酮为原料.黄酮氧苷的化学合成目前常用的方法有三种:Koening-Knorr法、相转移催化法、糖基三氯乙酰亚胺酯法.黄酮碳苷的糖苷链的连接主要是通过O→C重排法.酶催化生物合成法目前常用的酶是糖基转移酶和糖苷合酶这两种酶.
氟硼类荧光染料及其衍生物在肿瘤诊疗一体化中的应用
冯彤, 薛中博, 尹娟娟, 蒋旭, 冯亚青, 孟舒献
2019, 39(7): 1891-1912  doi: 10.6023/cjoc201812016
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肿瘤是全世界发病率最高、死亡率最大的疾病之一.鉴于肿瘤的高风险与高死亡率,世界各地的研究人员致力于开发更精确快速的诊断策略和更有效的治疗方法来对抗,针对肿瘤的光学诊疗一体化技术应运而生.氟硼荧类化合物(BODIPY)因其优良的光学性质在肿瘤光诊疗中被广泛关注.详细介绍了BODIPY及其衍生物作为光敏剂、光热转化剂及显影剂在肿瘤诊疗(光动力治疗、光热治疗、光声成像)以及诊疗一体化中的应用,全面系统地评价了不同BODIPY结构以及其衍生物在肿瘤诊疗中的效果.这对于合理设计具有高单线态氧量子产率、高光热转化率以及良好的光稳定性和溶解性等优点的近红外BODIPY材料具有重要意义.
抗肿瘤活性双四氢异喹啉生物碱类似物的合成研究进展
杨扬, 郭举, 刘站柱
2019, 39(7): 1913-1922  doi: 10.6023/cjoc201810037
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双四氢异喹啉天然产物是一大类具有较强生物活性的家族,目前已有近百个该类天然产物被陆续报道出来.自1974年Kluepfel等发现了第一个具有抗肿瘤活性的四氢异喹啉天然产物以来,已经有近百个该类四氢异喹啉天然产物被陆续报道出来,目前这类天然产物家族中的双四氢异喹啉生物碱因其优良的生物活性和复杂的化学结构成为了生物学和有机化学研究领域的热点,并进一步推动了该类天然产物家族成员Ecteinasicdin 743(ET-743)在欧盟成功上市,用于治疗晚期软组织瘤和卵巢癌.由于包括ET-743在内的这类双四氢异喹啉天然产物在自然界中含量极低以及化学结构复杂,使得对其化学结构的改造也引起了越来越多的关注.本文基于此,综述了近十年来这类双四氢异喹啉天然产物类似物的研究进展.
研究论文
氯胺-T促进的醛、肼与富马酸酯的三组分反应构建四取代吡唑类化合物
陈樱, 祝家楠, 赵圣印
2019, 39(7): 1923-1929  doi: 10.6023/cjoc201901014
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吡唑作为一种五元含氮杂环类化合物,不仅具有抗菌、抗肿瘤和抗氧化等生物活性,而且是一种重要的有机合成中间体,对其进行合成研究具有重要意义.以醛和肼作为腙的反应前体,研究了氯胺-T促进的醛、肼与富马酸酯的[3+2]环加成反应,对反应条件进行了优化,合成了四取代吡唑类化合物,收率在60%~87%之间,其结构经1H NMR、13C NMR、IR、HRMS等进行了确证.
4-氨基-5-取代-1, 2, 4-三唑-3-硫酮席夫碱的合成、生物活性及分子对接
武少婕, 卢一鸣, 雷卓楠, 蒋演, 张文慧, 齐乐, 马海霞, 任莹辉
2019, 39(7): 1939-1944  doi: 10.6023/cjoc201811016
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首先分别以硫代甲酰肼与冰乙酸为原料合成了中间体4-氨基-5-甲基-1,2,4-三唑-3-硫酮(M1);以取代苯甲酸为原料经过酯化、酰肼化、成盐和环化合成了中间体4-氨基-5-芳基-1,2,4-三唑-3-硫酮(M2).再将M1M2分别与4,6-二氯-5-嘧啶甲醛进行加成-消除反应,合成了4种新型含嘧啶环的1,2,4-三唑席夫碱化合物M1-1M2-1M2-2M2-3.通过元素分析、红外光谱分析及1H NMR对其进行结构表征.采用菌丝生长速率法及分子对接法研究目标化合物的生物活性及抑菌机理.结果表明,化合物对不同真菌均有一定的抑制作用.由EC50值可见,化合物M1-1M2-2M2-3对小麦赤霉菌的抑菌效果均优于标准药物(氟康唑),且与分子对接结果相一致.
Amberlyst-15催化下的二氢[1, 2, 4]三唑并[1, 5-a]嘧啶类及二氢苯并[4, 5]咪唑并[1, 2-a]嘧啶类衍生物的一锅法合成
马会芳, 李文博, 阿布拉江·克依木
2019, 39(7): 1945-1952  doi: 10.6023/cjoc201901050
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在固体酸性离子交换树脂Amberlyst-15的催化作用下,以乙醇作为溶剂,以芳香醛、β-酮酸酯、3-氨基-1,2,4-三唑或者2-氨基苯并咪唑为原料经过三组分一锅法反应合成了一系列三唑并[1,5-a]嘧啶衍生物5a~5m及二氢苯并[4,5]咪唑并[1,2-a]嘧啶类衍生物6a~6g.该方法简单高效、具有反应时间短、后处理简单、底物适用范围较广以及催化剂可以循环利用4次催化活性无明显下降的优点,符合绿色化学的基本标准.
基于芳基烯胺酯的环化反应合成苯并菲啶类似物及其细胞毒活性研究
王增博, 田成, 刘晴晴, 张玮, 潘成学, 苏桂发
2019, 39(7): 1962-1969  doi: 10.6023/cjoc201811004
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苯并菲啶生物碱具有抗肿瘤、抗病毒、抗炎及抗菌等广泛生物活性,因此其类似物的合成与活性研究引起了许多有机合成及药物化学研究者的兴趣.以3-异色酮及芳胺等为原料,以烯胺酯的环化反应为关键步骤,经3~4步反应合成了23个未见文献报道的苯并菲啶类似物,目标化合物结构经1H NMR,13C NMR和HRMS表征和确认.采用噻唑蓝(MTT)法测试了目标化合物对人肿瘤细胞MGC-803,HepG2,NCI-H460,SKOV3,T-24和人正常细胞HL-7702的体外细胞毒活性.发现只有很少量化合物对受试肿瘤细胞显示中等强度的增殖抑制活性,其中2,3-二甲氧基-6(1H)-异色并[4,3-c]喹啉(4j)对人膀胱癌细胞T-24和2-氯异色酮并[4,3-c]喹啉(5f)对人肺癌细胞NCI-H460的IC50值分别为15.8和16.7 μmol/L.
氮氧烯丙基正离子与肟的[3+3]环加成反应:2-N-无取代-1, 2, 4-噁二嗪-5-酮类化合物的合成
张智勇, 王琦, 张浩, 陈永明, 王欣, 葛泽梅, 李润涛
2019, 39(7): 1970-1975  doi: 10.6023/cjoc201901030
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首次实现了肟与氮氧烯丙基正离子的[3+3]环加成反应,为2-N-无取代-1,2,4-噁二嗪-5-酮类化合物的合成提供了一种有效方法.该方法具有原料易得、反应条件温和及收率高等优点.
8-异戊烯基黄酮类天然产物的微波促进Claisen重排合成
李蔚, 宿亮, 汪秋安, 李高阳, 单杨
2019, 39(7): 1976-1982  doi: 10.6023/cjoc201812020
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8-异戊烯基黄酮是一类具有显著生物活性的天然产物.以2,4,6-三羟基苯乙酮和3,4-二羟基苯甲醛为原料,用氯甲基甲醚保护羟基,经羟醛缩合、碘催化环合、过氧丙酮(DMDO)氧化、O-异戊烯基化、微波促进的Claisen重排、脱甲氧甲基保护基、O-甲基化和异戊烯基侧链环合等反应步骤,完成了8-异戊烯基槲皮素-3-甲醚(1)、8-异戊烯基槲皮素-3,7,3',4'-四甲醚(2)和Artochamin C(3)这3种8-异戊烯基黄酮类天然产物的合成.并对由微波促进的由5-O-异戊烯基黄酮类化合物合成8-C-异戊烯基黄酮类化合物的Claisen重排反应的关键步骤进行了探讨.所有合成的化合物经1H NMR、13C NMR和MS等结构确证.
基于二苯并24-冠-8桥联双柱[5]芳烃的线性和网状超分子聚合物
霍博超, 李斌, 苏杭, 曾宪强, 徐凯迪, 崔雷
2019, 39(7): 1990-1995  doi: 10.6023/cjoc201811003
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设计合成了一种二苯并24-冠-8桥联双柱[5]芳烃杂交主体1.利用含有2个5-(1,2,3-1H-三氮唑基)戊腈(TAPN)中性键合位点的双主题客体2与主体1中的柱[5]芳烃空腔的强络合构筑了AA/BB型的线性超分子聚合物.进而利用桥链冠醚部分与双主题二级铵盐客体3主客体包结自组装制备了三组分网状的超分子聚合物.通过对线性和网状聚合物进行1H NMR、黏度、DOSY、SEM等表征,结果表明超分子自组装体的形成呈现浓度依赖性,其线型超分子聚合物在氯仿/丙酮中(V:V=4:1)的溶剂中临界聚集浓度(CPC)为28 mmol/L.此研究设计了一种利用多次主客体相互作用构建高分子量聚合物的方法,为超分子聚合物的发展开辟了一条新的途径.
次氯酸钠引发的α-羟基酯的自由基氧化
王茂昌, 张宝华, 丁凯
2019, 39(7): 1996-2000  doi: 10.6023/cjoc201901019
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次氯酸钠是一种绿色氧化试剂,可用于醇的氧化,但是对a-羟基酯的氧化较为困难.发展了一种以次氯酸钠为氧化剂,氢溴酸为添加剂的氧化方法,可以快速高效地完成a-羟基酯化合物的氧化.进一步研究发现自由基是反应的中间体,与传统的Stevens氧化拥有不同的机理.该方法也可以用于普通醇的氧化,并且对多羟基化合物的氧化具有很好的选择性.
4, 4'-二甲氧基三苯胺取代偶氮苯开关分子的设计合成、电化学及光化学性质研究
鄢剑锋, 张睿祺, 原野, 袁耀锋
2019, 39(7): 2009-2017  doi: 10.6023/cjoc201902015
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通过Pd催化的Sonogashira偶联合成了三个以4,4'-二甲氧基三苯胺基团为氧化还原中心的偶氮苯化合物4~6,电化学和光谱电化学的研究表明,该类化合物具有优秀的氧化还原可逆性.光致异构的实验表明,三苯胺基团在偶氮苯上的取代位置对该类化合物的光化学性质有显著的影响.化合物4不仅可以通过光照实现顺式到反式的异构化,也可仅通过改变三苯胺基团的价态高效地实现.
基于Strecker反应的含氰基多取代吡唑的合成及生物活性研究
苏诗淼, 朱墨, 张大强, 袁德凯
2019, 39(7): 2026-2034  doi: 10.6023/cjoc201812019
[摘要]  (12) [HTML全文] (12) [PDF 558KB] (0)
摘要:
为探索多取代吡唑胺的Strecker反应及含氰基吡唑化合物的生物活性,首次实现了ZnI2催化下多取代吡唑胺、三甲基硅腈(TMSCN)和醛的Strecker反应,初步探索了反应条件及醛底物的范围.共获得20个全新含氰基多取代吡唑目标物,最高收率为93.5%,并通过核磁共振氢谱(1H NMR)、碳谱(13C NMR)和高分辨质谱(HRMS)确证了其结构.活性测试表明,10×10-3 g/L浓度下,13个化合物对蚊幼虫活性为100%,5×10-3 g/L浓度下4个化合物活性高于40%;在500×10-3 g/L浓度下10个化合物对黏虫体现一定活性.在500×10-3 g/L浓度下5个化合物对烟草花叶病毒具有一定钝化活性,最高活性为31.8%,4个化合物则具有保护活性,最高活性为28.3%.在50×10-3 mg/mL浓度下,3个化合物对瓜果腐霉菌、芦笋茎枯菌、辣椒疫霉菌、水稻纹枯菌等显示一定抑制活性,其中4-[(1-氰基十二烷基)氨基]-5-乙基-N-甲基-1H-吡唑-3-甲酰胺(3t)对辣椒疫霉活性达62.3%.这表明氨基邻位具有大位阻基团的吡唑胺底物能顺利发生Strecker反应,含氰基吡唑类目标物显示多样的生物活性,具有一定的研究价值.
Articles
A New Diarylethene Probe for Colorimetric Detection of CN- and Fluorescent Recognition of Zn2+/H2PO4-
Lu Diao, Renjie Wang, Niansheng Wang, Gang Liu, Shouzhi Pu
2019, 39(7): 1930-1938  doi: 10.6023/cjoc201901038
[摘要]  (12) [HTML全文] (12) [PDF 2295KB] (0)
摘要:
A new diarylethene 1-(3, 5-dimethylisoxazole-4-yl)-2-(2-methyl-5-[(3-aminonaphthol-2-yl)phenol-yl]-thiophene-3-yl)perfluorocyclopentene (1O) dual-response chemosensor has been synthesized, and its photochromic and fluorescent switch behaviors were systematically investigated by stimulation of lights and ions. The results indicated that 1O could serve as a CN-/F- "naked-eyes" colorimetric sensor with the color change from colorless to yellow, and act as a "Turn-on" fluorescence probe for specific detecting Zn2+. Moreover, the limits of detection of CN- and Zn2+ were determined to be 1.03×10-6 and 2.98×10-8 mol·L-1, respectively.
Synthesis and Biological Evaluation of Novel Phenylpropenoyl-amino Acid Derivatives
Sufan Gao, Yanchun Zhang, Jiaming Li, Bin Zhang, Yu Yang, Mengqi Hu
2019, 39(7): 1953-1961  doi: 10.6023/cjoc201812037
[摘要]  (11) [HTML全文] (11) [PDF 615KB] (0)
摘要:
Based on the listed drug rebamipide, a series of novel compounds of phenylpropenoyl-amino acid structures were designed and synthesized according to the pharmacophore-combination strategy. The structures of the target compounds were confirmed by NMR and MS. The inhibitory activities against IL-6 and TNF-α had been investigated. The results demonstrated that all compounds exhibited moderate IL-6 and TNF-α inhibitory activities. In particular, the activities of four compounds were significantly improved than that of rebamipide.
Design, Synthesis and Evaluation of Anti-tumor Activities of Chidamide Derivatives
Xiangna Zhang, Feng He, Qiuqiong Zhang, Jiahui Lü, A'na Xu, Chenggong Yu, Ying Qu, Jingde Wu
2019, 39(7): 1983-1989  doi: 10.6023/cjoc201812036
[摘要]  (16) [HTML全文] (16) [PDF 489KB] (0)
摘要:
A series of novel chidamide based histone deacetylases (HDACs) inhibitors were rationally designed and synthesized to increase the Zn2+ chelating and selectivity. Biological characterization established that most of the compounds showed moderate antiproliferative activitites in cancer cell lines. Among the tested analogs, (E)-N-(4-amino-6- fluoro-[1, 1'-biphenyl]-3-yl)-4-((3-(pyridin-3-yl)acrylamido)methyl)benzamide (7i) and (E)-N-(2-amino-4-fluoro-5-(thiophen- 2-yl)phenyl)-4-((3-(pyridin-3-yl)acrylamido)methyl)benzamide (7j) exhibit the most potent antiproliferative activity with IC50 of 3.29 and 2.59 μmol/L in Jurkat cells, respectively. Furthermore, these two compounds have a certain HDAC inhibitory activity. Collectively, the results partly encourage further development of more potential analogs based on chidamide.
One-Pot, Two-Step Reductive Amination of Boronate Ester Containing Aromatic Amines and Aldehydes Using B2pin2 as Reductant
Xueying Liu, Zhenwei Liu, Yuanyuan Guo, Jingya Li, Dapeng Zou, Yusheng Wu, Yangjie Wu
2019, 39(7): 2001-2008  doi: 10.6023/cjoc201902011
[摘要]  (9) [HTML全文] (9) [PDF 462KB] (0)
摘要:
The aromatic amine functionality occupies a very important role in organic chemistry due to its prominence in biological and naturally occurring molecules. In addition, the synthesized secondary aromatic amines with pendant boronate ester are versatile intermediates in several organic transformations. The one-pot, two-step reductive amination of boron-containing primary aromatic amines and aldehydes has been achieved in the presence of NaOH in ethanol using B2pin2 as reductant. After extensive screening of various reaction parameters, such as base, reaction temperature, solvent, reaction time and protective gas, a series of secondary aromatic amines with pendant boronate ester and various functional groups were obtained in moderate to good yields under the optimal reaction conditions. This system features generally high yields and broad functional group tolerance. The boronate ester substituent is a very good handle to be further functionalized.
Synthesis of Aldo-quinazolinones by Iodine-Induced Oxidative Condensation of Aldoses and o-Aminobenzamides
Huanhuan Ju, Jiajing Sun, Xiaoliu Li, Hua Chen
2019, 39(7): 2018-2025  doi: 10.6023/cjoc201901026
[摘要]  (11) [HTML全文] (11) [PDF 541KB] (0)
摘要:
A series of aldo-quinazolinones were synthesized by a one-pot iodine-induced oxidative condensation of the unprotected mono-/di-saccharides and o-aminobenzamides in the yields of 30%~80%, providing an effective protocol for the preparation of aldo-quinazolinones. The amount of iodine has an important effect on the reaction.
A Synthetic Route to Access Allyl-methyl-N-pantothenamide via [2,3]-Wittig Rearrangement
Liwen Xia, Qing Zhao, Mengyu Ba, chaoping Hu, Moran Sun, Hua Yang
2019, 39(7): 2035-2041  doi: 10.6023/cjoc201811009
[摘要]  (12) [HTML全文] (12) [PDF 526KB] (0)
摘要:
The synthetic route of allyl-methyl-N-pantothenamide (1) featuring[2,3]-Wittig rearrangement and palladium catalyzed formate reduction to assemble the requisite quaternary carbon with adjacent secondary alcohol has been reported. Our strategy presents a facile synthetic route to access 1 in 10 steps, which also provide a novel inspiration to construct chiral quaternary carbon via asymmetrical[2,3]-Wittig rearrangement.
研究简报
全氟烷基磺酰氟活化羧酸和1, 3-二羰基化合物之间一步O-酰基化反应
严兆华, 王彦梅, 金红爱, 艾城美, 田伟生
2019, 39(7): 2042-2047  doi: 10.6023/cjoc201901012
[摘要]  (12) [HTML全文] (12) [PDF 488KB] (0)
摘要:
碱性介质中,羧酸在全氟烷基磺酰氟活化下与1,3-二酮化合物和β-酮酸酯能发生一步O-酰基化反应,以中等到良好的产率生成相应的烯醇酯产物.
碘催化吲哚衍生物与二芳基二碲醚芳碲化反应制备3-芳碲基吲哚
陈锦杨, 胡丽, 汪海英, 谭红绘
2019, 39(7): 2048-2052  doi: 10.6023/cjoc201812045
[摘要]  (14) [HTML全文] (14) [PDF 441KB] (0)
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在20 mol% K2S2O8存在下,20 mol% I2催化吲哚衍生物与二芳基二碲醚反应,高产率获得一系列3-芳碲基吲哚化合物.该反应对不同吲哚衍生物和二芳基二碲醚均具有较好的适用性.此外,该方法具有反应条件温和、产率高、原子经济性等优点,为3-芳碲基吲哚化合物的制备提供高效的路径.
新型含1, 2, 4-三唑环结构的吡唑肟醚化合物的合成及其生物活性
王誉蓉, 郑丹丹, 王杨, 叶浩, 姚炜, 丁颖, 顾海鹰, 冯霞, 李玲, 戴红
2019, 39(7): 2053-2061  doi: 10.6023/cjoc201902027
[摘要]  (14) [HTML全文] (14) [PDF 508KB] (0)
摘要:
利用活性亚结构拼接原理,设计制备了18个未见文献报道的新型含1,2,4-三唑环结构单元的吡唑肟醚衍生物.通过1H NMR、13C NMR和元素分析等手段确认了其结构.初步的生物活性测试结果表明,部分目标化合物对粘虫、蚜虫和朱砂叶螨表现出良好的杀灭效果.在测试浓度为500 μg/mL时,目标化合物对粘虫的致死率在90%~100%,与对照药阿维菌素的杀虫效果相近,其中有4个化合物对蚜虫的致死率均为100%,与对照药吡虫啉的防效相当;1-甲基-3-甲基-5-(3,5-二氟苯氧基)-1H-吡唑-4-甲醛-O-[4-(1H-1,2,4-三唑-1-基)苯甲基]肟(8p)对朱砂叶螨的致死率为100%,与对照药唑螨酯的防效相当.当测试浓度降为100 μg/mL时,5个化合物对粘虫的致死率在90%~100%,3个化合物对蚜虫的致死率在80%~100%;化合物8p对朱砂叶螨的致死率为80%.当测试浓度降至20 μg/mL时,2个化合物对粘虫的致死率分别为75%和70%.另外,部分化合物对人肝癌(SMMC-7721)细胞显示出一定的抗肿瘤活性.
含肟醚的松油烯-4-醇衍生物的合成及杀虫活性
雷鹏, 丁新吉, 吴远勇, 马志卿
2019, 39(7): 2070-2074  doi: 10.6023/cjoc201812039
[摘要]  (20) [HTML全文] (20) [PDF 567KB] (0)
摘要:
为发现具有较高杀虫活性的先导化合物,结合本课题组前期研究结果,设计合成了系列含肟醚的松油烯-4-醇衍生物,并测试了杀虫活性.结果表明,目标化合物对粘虫具有较好的触杀作用,其中化合物2-甲基-5-异丙烯基-2-环己烯-1-酮肟-O-炔丙基醚(3a)的LD50值为0.0054 mg/头,毒力是松油烯-4-醇的19.1倍,可以作为农药先导化合物进一步优化研究.
温度对氮杂环卡宾催化下α-溴代烯醛与烯胺酮的[3+3]环化反应影响
王占林, 李如一, 钱辉旻, 姚昌盛
2019, 39(7): 2075-2083  doi: 10.6023/cjoc201901052
[摘要]  (19) [HTML全文] (19) [PDF 675KB] (0)
摘要:
氮杂环卡宾(NHC)催化下α-溴代烯醛和烯胺酮的[3+3]环化反应的区域选择性受温度控制.在35℃时,该反应能够区域专一性地给出稠合吡喃酮衍生物,而不是文献报道的喹啉酮类化合物.该方法反应条件温和、底物范围广、产率高、操作简便,为吡喃酮骨架的高效构建提供了新思路.
一种基于罗丹明类似物的Cys近红外荧光探针
田庆, 陈双虎, 陈景龙, 刘蕊, 汪雨诗, 杨晓朋, 叶勇
2019, 39(7): 2089-2093  doi: 10.6023/cjoc201812047
[摘要]  (9) [HTML全文] (9) [PDF 478KB] (0)
摘要:
基于罗丹明类似物作为荧光团合成了一例新型半胱氨酸(Cys)近红外荧光探针CS-Cys.该探针能特异性识别Cys,其他含巯基氨基酸不与探针响应,响应机理为:Cys与CS-Cys分子中的丙烯酸酯发生共轭加成-环化反应,进而羟基裸露并释放出荧光.通过对CS-Cys与Cys在不同pH环境中反应后的荧光变化进行研究,发现通过改变溶液pH值可调节给电子基的供电子能力和荧光团ICT过程,从而使荧光激发波长和发射波长达到近红外区域.
(±)-Parvistemonine A的全合成
马开庆, 任虎斌, 吴晓晓, 钞建斌, 秦雪梅
2019, 39(7): 2094-2098  doi: 10.6023/cjoc201901010
[摘要]  (15) [HTML全文] (15) [PDF 538KB] (6)
摘要:
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.
含噻唑联哌啶烟酰胺类化合物的合成与生物活性研究
丁成荣, 潘亚运, 殷许, 谭成侠
2019, 39(7): 2099-2105  doi: 10.6023/cjoc201812027
[摘要]  (10) [HTML全文] (10) [PDF 576KB] (0)
摘要:
噻唑联哌啶结构能够影响生物体内胆固醇类化合物的代谢活动,是氟噻唑吡乙酮抑制病原菌的氧胆固醇结合蛋白(OSBP)的关键药效基团.为了寻找具有生物活性的新型含噻唑联哌啶结构的化合物,设计并合成了14个未见文献报道的新颖含噻唑联哌啶烟酰胺类化生物,其结构经1H NMR、13C NMR和HRMS确证,生测结果显示:在100 μg/mL浓度下,目标化合物普遍具有抑菌活性,其中1个化合物对小麦赤霉病的抑菌活性为60%;3个化合物对黄瓜灰霉病的抑菌活性为60%;6个化合物对苹果褐斑病的抑菌效果为70%;(4-(5-(2,3-二氯苯基)-4-甲基噻唑-2-基)哌啶-1-基)(5,6-二氯吡啶-3-基)甲酮(6k)对马铃薯晚疫病的抑菌活性为75%.
新型石胆酸-3-肟酯衍生物及其蛋白酪氨酸磷酸酯酶1B抑制活性
侍术智, 梁志鹏, 孙建勇, 石玉军
2019, 39(7): 2106-2116  doi: 10.6023/cjoc201811020
[摘要]  (10) [HTML全文] (10) [PDF 1132KB] (0)
摘要:
蛋白酪氨酸磷酸酯酶1B(PTP1B)是治疗糖尿病的潜在靶标.内源性甾体化合物石胆酸具有温和的PTP1B抑制活性.将石胆酸3-OH氧化后,进一步修饰得到含有肉桂酸片段的石胆酸肟酯类衍生物,并通过1H NMR、13C NMR和HRMS鉴定其结构.生物活性筛选结果表明:所得目标化合物多数具有较强的PTP1B抑制活性,其中化合物12b的IC50达到0.79 μmol·L-1,是先导化合物石胆酸活性的15倍左右,同时该化合物对高度同源的T细胞蛋白酪氨酸磷酸酶(TCPTP)的选择性达到4倍左右.
Note
Synthesis and Fungicidal Activity of Novel Oxathiapiprolin Derivatives
Chengrong Ding, Yayun Pan, Xu Yin, Chengxia Tan, Xuedong Wang
2019, 39(7): 2062-2069  doi: 10.6023/cjoc201901009
[摘要]  (9) [HTML全文] (9) [PDF 492KB] (0)
摘要:
In order to explore the structure of lead compounds with biological activities, using oxathiapiprolin as a template, sixteen oxathiapiprolin derivatives were designed and synthesized to study the influences of substituent to the fungicidal activities which connected with carbon (No. 5 carbon) near the sulfur on the thiazole ring. All the structures were confirmed by 1H NMR, 13C NMR and HRMS. Preliminary bioassay showed that the target compounds generally had fungicidal activitives in vitro at a concentration of 100 μg/mL, the fungicidal activities of 1-(4-(4-cyclopropyl-5-(2-fluorophenyl)thiazol-2-yl)piperidin- 1-yl)-2-(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)ethan-1-one (9o) against Fusarium graminearum was 60%, the fungicidal activities of six target compounds against Diplocarpon mali were 70%, the fungicidal activities of four target compounds against Phytophthora infestans were 50%, and the fungicidal activities of 2-(5-methyl-3-trifluoromethyl-1H-pyrazol-1- yl)-1-(4-(4-methyl-5-(m-tolyl)thiazol-2-yl)piperidin-1-yl)ethan-1-one (9h) against Botrytis cinerea was 75%. In addtion, the fungicidal activities of the target compounds aganist Diplocarpon mali and Botrytis cinerea at 100 μg/mL were higher to azoxystrobin at 50 μg/mL.
Solvent-Free Aldol Reaction of β-Porphyrin Formaldehyde with Ketone
Xiang Zhou, Fei Zhou, Xiaoliang Jia, Jiawei Yu, Qi Shen, Yunxiao Zhang, Weimin Shi
2019, 39(7): 2084-2088  doi: 10.6023/cjoc201810004
[摘要]  (12) [HTML全文] (12) [PDF 479KB] (0)
摘要:
A convenient approach for the synthesis of β-substituted α, β-unsaturated carbonyl porphyrin compounds via base-catalyzed aldol reaction was developed. By this method, a series of β-substituted α, β-unsaturated carbonyl porphyrin compounds were constructed using β-porphyrin formaldehyde and ketones with moderate to excellent yields under mild reaction conditions, especially solvent-free, and good functional group tolerance. Furthermore, this process was successfully applied to the reactions of different metal porphyrin which have been reported to have poor reaction effects with good yields.
亮点介绍
亮点介绍(4)篇
2019, 39(7): 2117-2118
[摘要]  (12) [HTML全文] (12) [PDF 398KB] (1)
摘要:
ACCOUNT
Transition-Metal-Catalyzed Carbonylative Synthesis and Functionalization of Heterocycles
Zhiping Yin, Zechao Wang, Xiao-Feng Wu
2019, 39(3): 573-590  doi: 10.6023/cjoc201809004
[摘要]  (265) [HTML全文] (265) [PDF 1793KB] (265)
摘要:
Heterocycles are ubiquitous in natural products, pharmaceuticals, organic materials, and numerous functional molecules. These structural units probably constitute the largest and most varied family of organic compounds. Hence the development of new procedures for heterocycles synthesis has been a hot research topic for over centuries. Among all the new synthetic methods, transition-metal-catalyzed reactions are attractive. Those reactions can formulate complicated heterocycles efficiently from available starting materials under mild conditions and atom economical routes. Among them, transition-metal-catalyzed carbonylation reaction has become an efficient and useful tool in organic synthesis since the first hydroformylation reaction developed by W. Reppe at BASF in the 1930s. Since then impressive progress has been achieved in this area. In nowadays, various types of carbonylation reactions were established. Substrates including aryl halides, olefins, alkynes or simply C-H bond can be activated and produce the corresponding carbonyl-containing compounds smoothly. On the other hand, carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry around 80 years ago, academic and industrial laboratories have explored uses of CO in chemical reactions broadly. However, because of the special physical properties of CO, organic chemists were often reluctant to apply carbonylations frequently in laboratories. Hence, different kinds of CO surrogates were developed and applied in carbonylation reactions, such as metal carbonyl compounds M(CO)x, formates, alcohols, formic acid, aldehyde, biomass and carbon dioxide. Those CO surrogates offer interesting opportunities for carbonylation reactions. This account mainly outlines our progress in the development of transition-metal-catalyzed carbonylative synthesis and functionalization of heterocycles from 2012 to 2018. With copper, palladium, rhodium, ruthenium and iridium as the catalysts and relying on the activation of carbon-halogen and carbon-hydrogen bonds, we are able to synthesis various of heterocycles by using CO gas or CO surrogates as the C1 building blocks.
综述与进展
检测活性氮/活性氧的分子荧光探针
矫春鹏, 刘媛媛, 路文娟, 张平平, 王延风
2019, 39(3): 591-616  doi: 10.6023/cjoc201810013
[摘要]  (382) [HTML全文] (382) [PDF 1971KB] (382)
摘要:
活性氮和活性氧是具有强生物活性的化学物质.在人体细胞中,由于酶促或非酶促过程均可生成过氧化物,该物种的异常水平会引起氧化损伤与衰老和各种疾病,如心血管疾病、神经性疾病、阿尔茨海默病、帕金森病甚至癌症.因此,发展选择性识别和高灵敏度的分子荧光探针,实现活性氮或活性氧的有效检测具有重要意义.分子荧光探针检测法与成像技术具有灵敏度高、选择性强、损伤性小和细胞相容性好等优点,并在阐述活性氮和活性氧的病理生理过程中起到重要作用,在生物和医学等领域应用广泛.然而,由于活性氮和活性氧自身的特殊性而存在许多难题,例如反应活性高、存在周期短等一直困扰研究人员.着重综述了近年来发展的分子荧光探针用于活性氮和活性氧的检测及细胞成像工作的研究进展,提出进一步构建新型分子荧光探针用于活性氮和活性氧检测面临的挑战、未来发展方向及展望.
亚磺酸钠参与合成含硫化合物研究进展
黄国保, 李秀英, 罗金荣, 罗志辉, 谭明雄
2019, 39(3): 617-624  doi: 10.6023/cjoc201809030
[摘要]  (217) [HTML全文] (217) [PDF 602KB] (217)
摘要:
亚磺酸钠(RSO2Na)性质稳定、合成简单、价格低廉,在有机合成化学领域被广泛应用.综述了最近五年来亚磺酸钠在合成含硫化合物反应中的最新研究进展.分别叙述了其在有机反应中构建S-C键、S-杂键(S-S键、S-N键以及S-P键)的底物适应范围和反应机理,为今后亚磺酸钠的在有机合成中的应用提供参考.
烯烃的双官能团化反应研究进展
付晓飞, 赵文献
2019, 39(3): 625-647  doi: 10.6023/cjoc201808031
[摘要]  (426) [HTML全文] (426) [PDF 1035KB] (426)
摘要:
作为一类重要的有机化学反应,烯烃的双官能团化反应不仅可以经济有效地一步合成多位点反应产物,而且可以将起始原料转化为多种含有生物活性或药物活性的化合物,同时还为构建化学结构的多样性提供了更多的方法,所以发展烯烃的双官能团化反应十分重要.对近十二年来各类烯烃的双官能团化反应进行了综述.主要分为:铜催化的烯烃的双官能团化反应、其它过渡金属催化的烯烃的双官能团化反应以及非金属催化的烯烃的双官能团化反应.同时对该类反应的发展前景进行了展望.
聚乙二醇:绿色有机合成的新媒介
肖立伟, 戴富才, 李政, 景学敏, 孔洁, 刘光仙
2019, 39(3): 648-660  doi: 10.6023/cjoc201807056
[摘要]  (436) [HTML全文] (436) [PDF 811KB] (436)
摘要:
聚乙二醇(PEG)可以溶解多种有机物和金属配合物,具有良好的热稳定性、难挥发、无毒、能生物降解、廉价易得,易于回收和循环使用.PEG作为绿色介质已经成功地应用到许多有机反应中,如碳-碳偶联反应、碳-杂偶联反应、多组分反应、缩合反应、加成反应、取代反应、氧化反应、还原反应等.总结了近年来PEG作为反应介质在不同有机反应中的应用情况.
铜催化下含氮化合物的Chan-Lam偶联反应的研究进展
段希焱, 刘宁, 王佳, 马军营
2019, 39(3): 661-667  doi: 10.6023/cjoc201808015
[摘要]  (265) [HTML全文] (265) [PDF 567KB] (265)
摘要:
构筑碳-氮键在有机合成和药物化学领域有着重要的意义.近年来关于碳氮键合成反应的研究取得了长足的进展.其中铜催化的Chan-Lam偶联反应是构筑碳氮键最有效和直接的方式之一.系统综述了近十多年Chan-Lam偶联反应直接构筑C-N键的催化机理、反应体系、底物范围及结构特点等.
化学-酶多步串联反应及其在高附加值手性化合物高效、绿色合成中的应用
廖旭, 蒋岩, 赖石林, 刘源岗, 王士斌, 熊兴泉
2019, 39(3): 668-678  doi: 10.6023/cjoc201807038
[摘要]  (297) [HTML全文] (297) [PDF 882KB] (297)
摘要:
与化学催化或酶催化合成相比,化学-酶相结合的多步串联反应是一种更简单、高效、经济的方法,兼具酶催化剂的高效、高选择性等优点,且合成原料价廉易得,合成工艺简捷高效,生产环境绿色友好,所得产品光学纯度高,使其在高附加值手性化合物的开发和合成方面得到了广泛的应用.近年来,化学家们通过改变催化剂和设计更为合理的反应方式,致力于将化学-酶催化反应条件变得更为容易,从而将其应用于更多反应领域.综述了近年来国内外化学-酶多步串联反应,如酶与金属催化、酶与有机催化、酶与新型反应技术等相结合多步串联合成手性醇类、环氧类、杂环类以及其他手性化合物的研究进展,并对该领域的发展趋势进行了展望.
菲并咪唑类衍生物蓝光材料的研究进展
邱志鹏, 谭继华, 蔡宁, 王凯, 籍少敏, 霍延平
2019, 39(3): 679-696  doi: 10.6023/cjoc201807007
[摘要]  (225) [HTML全文] (225) [PDF 1560KB] (225)
摘要:
即将出现的全球能源危机和低效的能源利用推动了节能设备在显示和照明领域中的应用.节能的有机发光二极管被认为是新一代智能显示器,成为未来节能照明光源最具竞争力的候选产品之一.而高效深蓝色材料的分子设计由于其固有的宽带隙,载流子电荷传输不平衡以及其在固态下的低效率,发展受到很大限制.菲并咪唑基团作为一种新型蓝光材料的构筑单元,具吸引力的双极特性和优异的荧光效率,引起了科研工作者的强烈兴趣.对于菲并咪唑基团深蓝光材料的分子设计及其光物理性能研究具有重要的意义.综述了近几年来含有菲并咪唑类基团蓝光材料的发展状况,对菲并咪唑基团衍生物电致发光器件的发光机理、设计思路与最新进展进行了综述,并对其在未来全彩显示和固态照明领域上的前景进行了展望.
研究论文
一种黄酮荧光探针对肼的识别及细胞成像
鞠志宇, 舒朋华, 谢智宇, 蒋雨晴, 陶伟杰, 许志红
2019, 39(3): 697-702  doi: 10.6023/cjoc201808035
[摘要]  (192) [HTML全文] (192) [PDF 1248KB] (192)
摘要:
以邻羟基苯乙酮和对甲基苯甲醛为原料,合成了合成了一种3-羟基黄酮酯化物HFBA.通过探针HFBA对N2H4的识别性质研究,结果表明,探针HFBA在二甲亚砜-水溶液[V(DMSO):V(H2O)=7:3,PBS 20 mmol/L,pH=7.4]中对N2H4具有良好的选择性和灵敏度,且响应快速,抗干扰能力强,其检测限为0.11 μmol/L.细胞成像实验表明,探针HFBA可用于细胞内N2H4的检测.
Sc(Ⅲ)催化胺对邻亚甲基苯醌氮杂迈克尔加成反应合成贝蒂碱衍生物
张硕, 赵宁, 李庆刚, 张嘉祺, 侯梓桐, 刘一帆, 于一涛, 彭丹, 王峰, 李冰, 李金辉
2019, 39(3): 709-719  doi: 10.6023/cjoc201808045
[摘要]  (206) [HTML全文] (206) [PDF 561KB] (206)
摘要:
邻亚甲基苯醌化合物是一类非常活泼和重要的中间体,被广泛应用于天然产物和药物化学中.以2-[羟基(苯基)甲基]苯酚类化合物和胺为原料,1,2-二氯乙烷为溶剂,在Sc(Ⅲ)促进下原位生成邻亚甲基苯醌,并发生氮杂迈克尔加成反应合成贝蒂碱衍生物.反应在封管条件下90℃搅拌4 h完成,以76%~96%的产率得到目标产物.
基于新型帆船型络合物的超分子组装
张世龙, 蒋腊生
2019, 39(3): 720-726  doi: 10.6023/cjoc201810001
[摘要]  (217) [HTML全文] (217) [PDF 2553KB] (217)
摘要:
由于二芳基冠醚独特的大环型空腔结构及其对于客体分子的良好络合能力,利用分子内氢键成功设计了一类新型的、可通过酸碱控制其构型的帆船型自身络合物,对其进行了超分子组装,进而合成了一种新型索烃.通过利用分子间的电荷转移相互作用,以主体:客体=1:1的模板法,合成了一类新颖的索烃,利用了1H NMR、13C NMR、HRMS和1H-1H NOESY表征了其结构,希望通过改变酸碱环境控制其驱动.
铑/锌共催化苯酚对氧杂苯并降冰片烯的不对称开环反应研究
和振秀, 周永云, 孙蔚青, 樊瑞峰, 沈国礼, 樊保敏
2019, 39(3): 754-760  doi: 10.6023/cjoc201808027
[摘要]  (159) [HTML全文] (159) [PDF 467KB] (159)
摘要:
通过研究发现[Rh(COD)Cl]2/ZnI2/(2R,4R)-(+)-2,4-bis(diphenylphosphino)pentane作为共催化体系,能有效地催化酚类亲核试剂对氧杂苯并降冰片烯的不对称亲核开环反应,获得较好的收率和良好的对映选择性.在优化后的反应条件下,该共催化体系具有良好的催化活性和底物适应能力,能够实现各种取代的酚类亲核试剂对氧杂苯并降冰片烯的不对称开环,高效而又经济地合成不同取代的含手性四氢萘结构单元的化合物.
稠合四环噻嗪烷-4-酮衍生物的合成及其抗肿瘤活性
牛丽萍, 邢顺凯, 李小六, 陈华
2019, 39(3): 771-777  doi: 10.6023/cjoc201807043
[摘要]  (182) [HTML全文] (182) [PDF 814KB] (182)
摘要:
以叔丁氧羰基(Boc)保护的脯氨醛1、氨基酸酯盐酸盐2a~2d和巯基水杨酸3a~3b为原料,三组分一锅法得到苯并噻嗪烷-4-酮中间体.酸性条件下脱除Boc,分子内酰胺缩合制备稠合四环噻嗪烷-4-酮衍生物6~11.新生成手性碳(1-C)的构型通过H-1和H-2的偶合常数及X-ray单晶衍射确定.测试了化合物抗Hela和A549的肿瘤细胞增殖活性.结果表明,部分化合物具有中等的抗Hela细胞活性,其中(13aR,13bR)-1,2,3,13b-四氢苯并[e]吡咯并[2',1':3,4]吡嗪并[2,1-b][1, 3]噻嗪-5,8(6H,13aH)-二酮(6b)的IC50值为9.50 μmol/L.所有化合物对A549的细胞没有抑制活性.
寨卡病毒抑制剂的虚拟筛选、设计、合成及生物活性研究
李彦忠, 齐思佳, 徐彦浩, 夏成才, 段桂运
2019, 39(3): 786-792  doi: 10.6023/cjoc201807053
[摘要]  (194) [HTML全文] (194) [PDF 3978KB] (194)
摘要:
由甲基转移酶和RNA聚合酶组成的多功能蛋白(NS5)是寨卡病毒复制过程中起主要作用的蛋白组分,其甲基转移酶(5M5B)部分是病毒复制和宿主固有免疫应答的中心参与者,因此被作为潜在抗寨卡病毒药物开发的首选靶标蛋白.将5M5B作为受体,利用其已知的结合位点与200多万个化合物小分子进行虚拟筛选,得到抗寨卡病毒的先导化合物2a,并对该先导化合物进行结构优化、改造、活性预测、化学合成、药理活性研究.使用1H NMR和13C NMR对所有合成的化合物进行了表征,并进行了体外活性测试.结果表明化合物3a[IC50=(7.69±0.36)μmol·L-1]的体外活性优于广谱抗病毒药利巴韦林活性[IC50=(8.15±0.42)μmol·L-1],本研究的方法与结果对寨卡病毒抑制剂的结构设计研究具有重要的指导作用.
系列红色染料的合成、光学性质及在蛋白标记中的应用
李慧芳, 冷鑫, 闫立润, 杨秉勤, 白银娟
2019, 39(3): 793-799  doi: 10.6023/cjoc201807036
[摘要]  (180) [HTML全文] (180) [PDF 2437KB] (180)
摘要:
以3-NN-二乙基氨基酚为原料合成了一系列荧光染料,用1H NMR,13C NMR,IR,HRMS对结构进行了表征,检测了新型染料的光学性质,标记了牛血清白蛋白,比较了新染料与菁染料(Cy3)在凝集素微阵列芯片上的荧光信号值.结果显示,新型染料的最大发射波长均在600 nm以上,斯托克斯位移约70 nm左右,染料/蛋白质(D/P)标记效率高达1.5~1.8,在凝集素微阵列中新染料和Cy3的荧光信号值相当.表明新染料可以作为荧光标记物用于凝集素微阵列中检测糖链的变化.
ARTICLES
Synthesis and Evaluation of Chalcone Derivatives as Novel Anticancer Agents
Qiwei Sheng, Wanqiu Zhao, Ming Zeng, Zhongpao Xie, Yaping Xia, Dongmei Cui
2019, 39(3): 703-708  doi: 10.6023/cjoc201808037
[摘要]  (163) [HTML全文] (163) [PDF 456KB] (163)
摘要:
Three series of chalcones bearing a piperidino, morpholino, and 1-methylpiperazino moiety were synthesized in two steps with the key step being Claisen-Schmidt condensation and tested for the activity against five cell lines, MCF-7 (human breast adenocarcinoma cell line), A549 (human lung adenocarcinoma epithelial cell line), HL-60 (human leukemia cell line), Hela (human cervical cancer cell line), and Bewo (human chorionic tumor cell line) by thiazolyl blue tetrazolium bromide (MTT) assay. Some chalcones exhibited good anticancer activity, and among them 4a, 4e, 4f, 4j, 4m, and 4o displayed the best anticancer activity for MCF-7 breast cancer cells, A549 lung cancer cells, and HL-60 leukemia cancer cells with IC50 values below 10 μmol/L, respectively.
Research on Reduction of α, α, α-Tribromomethyl Ketones via Thiophenol
Ying Yang, Hasimujiang Balati, Abudu Rexit Abulikemu
2019, 39(3): 727-733  doi: 10.6023/cjoc201810003
[摘要]  (177) [HTML全文] (177) [PDF 401KB] (177)
摘要:
α, α-Dibromomethyl ketones were synthesized with high yields through a thiophenol-promoted reduction of α, α, α-tribromomethyl ketones under mild conditions within one hour. A further mechanistic study showed that the reaction proceeded via a radical process. This is an example that uses thiophenol as the radical stimulator in the reduction of multi-halogenated compounds.
Nano-Gold Catalyzed Transesterification of (Hetero) aryl Esters with Alkyl Halides via C-O Activation
Hongpeng Ma, Chaolumen Bai, Yongsheng Bao
2019, 39(3): 734-746  doi: 10.6023/cjoc201809027
[摘要]  (144) [HTML全文] (144) [PDF 1491KB] (144)
摘要:
Nano-gold catalyzed transesterification of the (hetero) aryl ester with alkyl halides via C-O activation has been developed. In a series of supported AuNPs and PdNPs, the Au/γ-Al2O3 catalyst with an AuNP mean diameter of 3.63 nm and 3 wt% Au loading exhibited the best catalytic performance. The catalyst can be reused and shows high activity after five cycles. The X-ray photoelectron spectroscopy (XPS) analysis of the catalyst before and after the reaction suggested that the reaction might be performed via a catalytic cycle that began with Au0.
Synthesis, Biological Evaluation, and Structure-Activity Relationship Study of Unsaturated Spiroacetals as Potential Sex Attractants to Oriental Fruit Flies (Bactrocera dorsalis)
Jiuyi Li, Li Chen, Biaolin Yin
2019, 39(3): 747-753  doi: 10.6023/cjoc201808022
[摘要]  (162) [HTML全文] (162) [PDF 475KB] (162)
摘要:
Spiroacetal motif is widely distributed in many bioactive natural products of different origins and essentially contributes to various bioactivities. In this paper, two series of spiroacetals were synthesized and biologically evaluated as insect sex attractant towards oriental fruit flies (Bactrocera dorsalis) using methyleugenol as the standard. Biological evaluation demonstrated that a large part of the tested compounds triggered apparent electrophysiological responses from both male and female fruit flies. The stereochemistry of the spiroacetals and the substitution on their phenyl rings influenced the responses to some degree.
Synthesis and Applications of Excimer Host Materials Based on 2, 4, 6-Triphenyl-1, 3, 5-triazine and Fluorene Moieties
Xu He, Yuping Xiao, Xinlei Yuan, Shanghui Ye, Hongji Jiang
2019, 39(3): 761-770  doi: 10.6023/cjoc201806017
[摘要]  (164) [HTML全文] (164) [PDF 1319KB] (164)
摘要:
Three new bipolar derivatives based on 2, 4, 6-triphenyl-1, 3, 5-triazine and fluorene moieties, namely FTRZ, pTFTRZ and mTFTRZ were designed and synthesized by using 9-(4-(hexyloxy) phenyl) -9H-fluorene, 2-bromo-4, 6-diphenyl-1, 3, 5-triazine, 2, 4, 6-tris(4-bromophenyl) -1, 3, 5-triazine, and 2, 4, 6-tris(3-bromophenyl) -1, 3, 5-triazine through palladium-cata-lyzed cross-coupling reaction, which were reported as hosts for thermally activated delayed fluorescence organic light-emitting diodes (OLEDs). The 1H NMR, 13C NMR and MALDI-TOF-MS spectra were used to characterize the chemical structure of compounds FTRZ, pTFTRZ and mTFTRZ. Their thermal, photophysical and electrochemical properties as well as electroluminescent device performance were thoroughly investigated to correlate the optoelectronic properties with the topology-varied molecular structure. The thermal decomposition temperatures of compounds FTRZ, pTFTRZ and mTFTRZ are 427, 446 and 424℃ and their glass transition temperatures of compounds pFTRZ and mTFTRZ are 120 and 103℃, respectively. The optical band gaps of compounds FTRZ, pTFTRZ and mTFTRZ in toluene solution are 3.24, 3.29 and 3.24 eV, and their triplet energy levels are 3.04, 3.11 and 3.05 eV, respectively. Due to the π-π interaction between 2, 4, 6-triphenyl-1, 3, 5-triazine planes, compounds FTRZ, pTFTRZ and mTFTRZ form excimer in the thin film state. The electroluminescent properties of OLEDs using compounds FTRZ, pTFTRZ and mTFTRZ as the hosts and 2, 4, 5, 6-tetrakis(carbazol-9-yl) -1, 3-dicyanobenzene as the guest emitter were investigated. The green OLED of compound FTRZ as host material shows a peak emission at 510 nm with a maximum current efficiency of 6.7 cd/A, a maximum external quantum efficiency of 2.07% and a maximum brightness of 35718 cd/m2. The efficiency roll-offs of the OLEDs hosted by compounds FTRZ and pTFTRZ at 20000 cd/m2 are 3% and 2%, which are much better than the same device hosted by compound mTFTRZ.
Design, Synthesis and Evaluation of Novel Gd-Based 1, 4, 7, 10-Tetraazacyclododecan-N, N', N, N'-tetraacetic Acid-Hydrazide Derived Contrast Agents for Magnetic Resonance Imaging
Hongshun Sun, Jin Zhou, Yulong Li, Hong Jiang, Yan Zhang, Jianqiang Wang, Cheng Guo, Linjiang Shen
2019, 39(3): 778-785  doi: 10.6023/cjoc201808005
[摘要]  (152) [HTML全文] (152) [PDF 1706KB] (152)
摘要:
Magnetic resonance imaging (MRI) is widely used in diagnostic medicine and soft tissue imaging. Contrast agents (CAs) can improve the specificity of MRI enhancement. Herein, the design, synthesis and characterization of twelve novel Gd-based 1, 4, 7, 10-tetraazacyclododecan-N, N', N, N'-tetraacetic acid (DOTA) -hydrazide derived contrast agents for MRI were reported. Among of them, 5d, 5h and 5l exhibit higher longitudinal relaxivities than the clinical Gd-DOTA at 0.5 T. The relaxivities r1 of 5d, 5h and 5l are 4.67, 4.85 and 5.33 L·mmol-1·s-1 respectively. In vivo liver-target MRI shows that the potential of complex 5d was used as a novel liver-target contrast agent for MRI.
ARTICLE
Chemoselective Synthesis of Substituted Benzoxazines and Imidazolidines by Reactions of Hydroxyl Substituted Ethylenediamine Derivatives with Aldehydes
Zilong Tang, Ming Wang, Yuan Yao, Jingzhao Tan, Ningning Dai, Xinxing Li, Lifen Peng, Yinchun Jiao
2019, 39(3): 800-810  doi: 10.6023/cjoc201808003
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摘要:
Lewis acid La(OTf) 3-catalyzed chemoselective cyclization of hydroxyl substituted ethylenediamine derivatives with aldehydes has been described for the first time, which provides efficient access to diversely functionalized 1, 3-imidazoli-dines and 3, 1-benzoxazines in generally good yields only by adjusting the position of the methylene group within hydroxyl substituted ethylenediamines. The reaction is suitable to aromatic aldehydes and aliphatic ones. Plausible mechanisms are also proposed to explain the observed reaction modes, wherein the nucleophilicity of nitrogen and oxygen atoms plays an important role in controlling the chemoselectivity.
α-Oxygenation of Benzylic Ethers to Esters Using MnOx-N@C Catalyst
Jing Liu, Cong Wan, Aili Zheng, Lianyue Wang, Kaiyue Yin, Dandan Liu, Shengde Wang, Lanhui Ren, Shuang Gao
2019, 39(3): 811-820  doi: 10.6023/cjoc201807011
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摘要:
A catalytic system for the oxidation of benzylic ethers to esters has been developed utilizing reusable MnOx-N@C as catalyst and tert-butyl hydroperoxide (TBHP) as benign oxidant under neat condition. The catalytic oxidation system has good functional groups tolerance and excellent chemoselectivity, and this catalytic procedure can also be scaled up.
Synthesis and Antitumor Activity of Novel Isolongifolic-Alkyl Dihydropyrimidinethione Derivatives
Chonghui Ma, Chenliang Wu, Yunyun Wang, Zhenzhen Huang, Qiangjian Zhang, Fuhao Dong, Wen Gu, Yu Shan, Shifa Wang
2019, 39(3): 821-829  doi: 10.6023/cjoc201807022
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摘要:
In this work, twelve dihydropyrimidinethione derivatives have been synthesized from isolongifolanone by aldol and cyclization reactions. The chemical structures were characterized by 1H NMR, 13C NMR and high resolution mass spectrometry (HRMS), and the structure of compound 3e was determined by X-ray single crystal diffraction. Their in vitro cytotoxicity against three cancer cell lines breast (MDA-MB-231), cervix (HeLa), liver (HepG-2) and one normal cell line mouse macrophages (Raw-264.7) were investigated. It was shown that these 12 compounds had good antitumor activity with IC50 values of 3.12~44.28 μmol/L. Among them, compounds 3j, 3g, and 3k had the best antitumor activity against MDA-MB-231 cells (IC50=3.12 μmol/L), HeLa cells (IC50=4.04 μmol/L) and HepG-2 cells (IC50=5.43 μmol/L), respectively. In addition, compound 3j arrested the cells in the G0/G1 phase of the MDA-MB-231 cell cycle and induced the early apoptosis of MDA-MB-231 cells in a dose-dependent manner.
研究简报
钯催化下稳定磷叶立德与烯丙基醇的脱水偶联反应
马献涛, 于静, 马瑞甜, 燕然, 张振雷
2019, 39(3): 830-835  doi: 10.6023/cjoc201812051
[摘要]  (232) [HTML全文] (232) [PDF 502KB] (232)
摘要:
报道了钯催化下酮基稳定的磷叶立德与烯丙基醇一锅法的烯丙化-Wittig反应.研究表明,在5 mol%四(三苯基膦)钯和20 mol%硼酸的共催化下,以52%~95%的收率得到官能化1,4-二烯化合物.该方法还可以进一步拓展到酯基以及氰基稳定的磷叶立德来合成对应的1,4-二烯化合物.
新型哌啶噻唑类化合物的合成及杀虫活性
丁成荣, 潘亚运, 殷许, 谭成侠, 张国富
2019, 39(3): 836-841  doi: 10.6023/cjoc201809009
[摘要]  (168) [HTML全文] (168) [PDF 570KB] (168)
摘要:
为了探寻新型的生物活性化合物,设计并合成了12个未见文献报道的新型哌啶噻唑类衍生物.生物活性测试研究发现,在500 μg/mL浓度下,目标化合物对粘虫表现出良好的抑制活性,而且在100 μg/mL下,(4-(5-(3-氯苯基)-4-甲基噻唑-2-基)哌啶-1-基)(4-甲基哌嗪-1-基)甲酮(1f)、(5-(3-氯苯基)-4-甲基噻唑-2-基)哌啶-1-基)(4-硝基-1H-吡唑-3-基)甲酮(1g)对粘虫的抑制率均达80%以上,另外在20 μg/mL下(5-(3-氯苯基)-4-甲基噻唑-2-基)哌啶-1-基)(4-硝基-1H-吡唑-3-基)甲酮(1g)仍具有50%的杀虫活性.
砂贝母中异甾体生物碱类成分的研究
黄金昌, 雷春, 阿吉艾克拜尔·艾萨, 俞媚华, 阿布力米提·伊力, 侯爱君
2019, 39(3): 842-847  doi: 10.6023/cjoc201809019
[摘要]  (142) [HTML全文] (142) [PDF 1609KB] (142)
摘要:
利用各种柱色谱和高效液相色谱等分离纯化方法,从砂贝母鳞茎中分离得到6个异甾体生物碱类化合物.根据质谱、一维/二维核磁共振谱和X射线单晶衍射等技术鉴定了它们的结构,分别为karelinine(1),5-epikarelinine(2),27-epiebeienine(3),ebeienine(4),persicanidine B(5)和heilonine(6),其中化合物1~3为新化合物.化合物1是贝母属中罕见的5β-jervine型异甾体生物碱,具有A/B环顺式稠合方式.化合物12也是贝母属中首次发现的具有15α-OH取代的jervine型生物碱.
纤枝金丝桃中3个新多环多异戊烯基间苯三酚类成分
王扣, 王赟, 王子明, 丁林芬, 胡建林, 陈佳
2019, 39(3): 848-851  doi: 10.6023/cjoc201807059
[摘要]  (142) [HTML全文] (142) [PDF 719KB] (142)
摘要:
利用多种色谱分离方法对纤枝金丝桃的化学成分进行研究,从其甲醇提取物的石油醚萃取部位分离得到3个新化合物,其结构经HRMS,1D和2D NMR等多种现代波谱鉴定为hyperlagarin A(1)、hyperlagarin B(2)和hyperlagarin C(3).
新型4-芳氨基嘧啶类衍生物的合成及其杀虫活性
吴宁捷, 程龙, 王剑, 郁季平, 邢家华, 许天明, 魏优昌
2019, 39(3): 852-860  doi: 10.6023/cjoc201807044
[摘要]  (143) [HTML全文] (143) [PDF 535KB] (143)
摘要:
以取代苯胺为起始原料,经重氮化、Meerwein芳基化、异硫氰化、加成、甲基化、环化等多步反应合成一系列结构新颖的4-芳氨基嘧啶类衍生物,并测试了目标化合物的杀虫活性.初步杀虫活性结果表明,在质量浓度500 mg/L时,大部分化合物对粘虫的致死率为100%;当质量浓度降至20 mg/L时,2-甲基-4-[N-(2-氯-4-氟苯基)氨基]-5-[2-三氟甲基-4-(苯氧基)苯基]-6-甲基嘧啶(6h)对粘虫和小菜蛾的致死率分别为80%和60%.
3-(((3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)亚甲基)氨基)取代苯并[d][1, 2, 3]三嗪-4(3H)-酮类化合物的合成及生物活性
张燕, 朱洪伟, 尚俊峰, 王宝雷, 李正名
2019, 39(3): 861-866  doi: 10.6023/cjoc201808033
[摘要]  (160) [HTML全文] (160) [PDF 528KB] (160)
摘要:
N-吡啶基吡唑甲酸乙酯、取代邻氨基苯甲酸为原料,经由还原、氧化、亲核加成、缩合、重氮化等多步反应,合成了一系列3-(((3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)亚甲基)氨基)取代苯并[d][1,2,3]三嗪-4(3H)-酮类目标化合物.初步生物活性测试结果表明,该系列化合物大多具有一定的杀虫活性,其中一个化合物在200 mg·L-1浓度下对东方粘虫(Mythimna separata Walker)具有70%的致死率;部分化合物表现出显著的抑菌活性,有两个化合物在50 mg·L-1浓度下对苹果轮纹病菌(Physalospora piricola)具有92.3%的抑制率,可作为新型抑菌先导结构,为后续的深入研究提供重要参考.
N-烷氧基取代酰胺类化合物的合成及杀菌活性
黄朋勉, 周智慧, 杜永磊, 庞怀林, 吕亮
2019, 39(3): 867-872  doi: 10.6023/cjoc201806029
[摘要]  (141) [HTML全文] (141) [PDF 494KB] (141)
摘要:
为寻找具有高杀菌活性的农药先导化合物,采用活性亚结构拼接的方法,将吡唑醚菌酯结构中羟基吡唑结构片段引入氟唑菌酰羟胺的结构中,合成了12个结构新颖的N-烷氧基酰胺类化合物.目标化合物的结构经过1H NMR,13C NMR和HRMS确证.杀菌活性测试表明,在测试浓度下,一些目标化合物对亚洲大豆锈病、黄瓜霜霉病或黄瓜白粉病表现出了一定的防效,其中化合物3a在100 mg/L测试浓度下对黄瓜白粉病的防效为95%.
Note
Efficient, Solvent-Free Aminolysis of Monoesters Catalyzed by Sodium
Tao Shen, Bo Ouyang, Shaodong Zhou, Chao Qian, Xinzhi Chen
2019, 39(3): 873-877  doi: 10.6023/cjoc201808006
[摘要]  (190) [HTML全文] (190) [PDF 414KB] (190)
摘要:
An efficient, solvent-free procedure using sodium as catalyst for the aminolysis of monoesters is reported. A detailed comparison of catalysts between sodium and sodium amide was made. It was found that the fresh sodium amide by in-situ synthesis of sodium with ammonia was more active than the indirectly adding sodium amide. As compared to the previously reported approaches, the procedure given in this work is much faster and performed under mild conditions. Furthermore, this procedure is applied successfully for the aminolysis of other monoesters.
亮点介绍
亮点介绍(8)篇
2019, 39(3): 878-881
[摘要]  (166) [HTML全文] (166) [PDF 500KB] (166)
摘要: