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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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]  (38) [HTML全文] (38) [PDF 1706KB] (0)
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
[摘要]  (37) [HTML全文] (37) [PDF 498KB] (0)
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
[摘要]  (50) [HTML全文] (50) [PDF 4056KB] (1)
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
[摘要]  (36) [HTML全文] (36) [PDF 1693KB] (0)
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]  (57) [HTML全文] (57) [PDF 502KB] (0)
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]  (48) [HTML全文] (48) [PDF 570KB] (0)
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]  (38) [HTML全文] (38) [PDF 1609KB] (0)
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]  (36) [HTML全文] (36) [PDF 719KB] (1)
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]  (35) [HTML全文] (35) [PDF 535KB] (1)
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]  (39) [HTML全文] (39) [PDF 528KB] (0)
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]  (37) [HTML全文] (37) [PDF 494KB] (1)
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]  (54) [HTML全文] (54) [PDF 414KB] (0)
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]  (39) [HTML全文] (39) [PDF 500KB] (1)
摘要:
综述与进展
基于氟烷基自由基过程构建手性中心的研究进展
黄航, 王兮, 王剑波
2019, 39(1): 1-14  doi: 10.6023/cjoc201808030
[摘要]  (202) [HTML全文] (202) [PDF 688KB] (202)
摘要:
含氟的有机化合物被广泛地应用于制药、农业化学品、材料科学等多个领域.三氟甲基、二氟甲基、全氟烷基等是应用非常广泛的含氟官能团,因此发展普适高效的引入氟烷基的新方法具有重大意义.氟烷基自由基反应近年来已经发展成为引入氟烷基的有效方法.另一方面,氟烷基取代的手性有机分子的合成也受到了人们的重点关注.然而由于氟烷基自由基的高反应活性,其反应的选择性较难控制,特别是关于对映选择性控制的报道不多,更缺乏相关综述予以总结.综述了近二十年来基于氟烷基自由基过程的不对称合成方法的研究进展,对各反应的选择性、普适性、反应机理等方面进行着重介绍.本综述根据反应机理分为三部分:(1)经由氟烷基自由基的烯醇/烯胺中间体不对称氟烷基化;(2)经由氟烷基自由基的烯烃不对称双官能团化;(3)经由氟烷基自由基的烯基硼酸酯酸根型复合物立体选择性1,2-迁移.
镍催化的烯丙基取代反应研究进展
张慧君, 顾庆, 游书力
2019, 39(1): 15-27  doi: 10.6023/cjoc201809037
[摘要]  (251) [HTML全文] (251) [PDF 808KB] (251)
摘要:
过渡金属催化的烯丙基取代反应是构建碳-碳键、碳-杂原子键的重要手段.由于镍价廉易得,适用性广,赢得了化学家们的广泛青睐.在过去50年里,关于镍催化的烯丙基取代反应的报道不断涌现.根据成键类型及亲核试剂的种类进行划分,总结近年来镍催化的烯丙基取代反应的进展及其在有机合成中的应用.
中国有机氟化合物卤键研究
刘传志, 王辉, 张丹维, 赵新, 黎占亭
2019, 39(1): 28-37  doi: 10.6023/cjoc201812026
[摘要]  (163) [HTML全文] (163) [PDF 3281KB] (163)
摘要:
综述了中国学者在有机碘代和溴代氟化物的卤键研究方面的进展.从1987至1993年,陈庆云等发现全氟碘代烷作为Lewis酸可以和胺、醚和六甲基磷酰胺等Lewis碱形成供体-受体相互作用,代表了早期研究现在被称为卤键的非共价键作用力的重要进展.2001年以来,多个研究组利用卤键开展晶体工程研究.朱士正等首次证实,全氟-αϖ-二碘烷烃可以和胺、醚和六甲基磷酰胺等通过卤键形成一维扩展阵列结构,晋卫军等研究了卤键驱动的全氟碘代芳烃与氮杂芳环的共晶结构,张丹维和黎占亭等利用卤键诱导产生了双螺旋及四螺旋超分子聚合物.晋卫军等研究了C—I…π卤键在晶体工程中的应用.利用卤键诱导,王栋和万立骏等在表面实现了三角型芳香分子共组装形成二维蜂窝型阵列结构,王力彦等从两个聚合物或有机分子构筑了单层膜结构和实现了层-层自组装控制.赵新和黎占亭等合成了并入三个二氟碘甲基的三臂分子,基于氢键诱导的折叠型受体,建立了溶液相多位点卤键结合的识别模式.胡文平、龚和贵、廖良生等利用卤键提高了若干共轭有机分子的不同的材料性能.多个研究组利用卤键成功控制或提高不同类型的有机反应的选择性.
过渡金属参与的C—F键官能团化反应机理研究进展
李园园, 王元鉴, 朱磊, 屈凌波, 蓝宇
2019, 39(1): 38-46  doi: 10.6023/cjoc201810020
[摘要]  (153) [HTML全文] (153) [PDF 852KB] (153)
摘要:
有机氟化学凭借其独特的内涵在材料科学、催化化学、医学、精细化工以及生物化学领域引起了越来越多的重视,其核心在于碳-氟键的构建和切断.过渡金属的引入为活化碳-氟键提供了新的可能,也逐渐成为合成很多复杂有机物的一种替代途径.总结了以往对过渡金属促进碳-氟键活化和切断的理论研究进展,并系统性提出了碳-氟键活化的相关模式,包括碳-氟键对金属的氧化加成、过渡金属活化的芳香亲核取代、碳(sp3)-氟键双分子亲核取代(SN2)以及β-氟消除等.理论计算表明,当使用还原性较强的零价镍催化剂时,反应可按照氧化加成模式启动.而如果使用零价铂催化剂,则需要对氟原子进行额外活化才能发生氧化加成.当使用氢化金属物种还原多氟代芳烃时,氢负离子可以与多氟代芳烃发生芳香亲核取代实现碳-氟键活化.对于碳(sp3)-氟键来说,如果使用“硬”的Lewis碱,例如锂盐或镁盐,则可按照双分子亲核取代(SN2)方式活化碳(sp3)-氟键.此外,β-氟消除也是一种可能的替代机理.
生物碱Peduncularine的合成策略和方法
章玉平, 田学超, 张岩, 洪然, 黄莎华
2019, 39(1): 47-58  doi: 10.6023/cjoc201810008
[摘要]  (187) [HTML全文] (187) [PDF 759KB] (187)
摘要:
(-)-Peduncularine是从塔斯玛尼亚灌木Aristotelia peduncularis中分离得到的生物碱,含吲哚结构单元且含有高张力的6-氮杂双环[3.2.1]辛烷核心骨架.由于其独特的结构,受到合成化学家的极大关注.目前,已有多个课题组对其展开了全合成研究.本文将介绍近年来不同研究小组所发展peduncularine的合成策略,对于药物合成研究中类似特殊环系的构建提供借鉴.
芳基三氟甲基酮类化合物的合成进展
张洁雨, 柯求敏, 陈家英, 何平, 严国兵
2019, 39(1): 74-83  doi: 10.6023/cjoc201808046
[摘要]  (147) [HTML全文] (147) [PDF 594KB] (147)
摘要:
芳基三氟甲基酮是一类非常重要的有机合成中间体.由于其具有潜在的生物活性,越来越引起研究者的广泛关注.综述了近年来芳基三氟甲基酮类化合物的合成,主要包括α-三氟甲基醇的氧化,羧酸衍生物的三氟甲基化,金属有机试剂、富电子芳烃,芳基卤化物、芳基重氮盐等的三氟乙酰化反应,以及其机理的探讨.
可见光促进的烯烃异构化反应
张昊, 俞寿云
2019, 39(1): 95-108  doi: 10.6023/cjoc201809010
[摘要]  (157) [HTML全文] (157) [PDF 1149KB] (157)
摘要:
传统合成热力学不稳定的Z-式烯烃的方法往往都需要使用高能量的试剂,通过动力学来进行控制,反应条件较为苛刻,操作复杂,原子经济性低下.在分离的过程中,也极易造成Z-式烯烃向热力学更加稳定的E-式烯烃的异构化.随着有机光化学和光催化技术的不断发展,越来越多的具有挑战性的有机合成反应可以通过有机光化学手段来解决.总结了可见光促进的烯烃的异构化反应,并对其进行了展望.
三氟甲基三氮唑及四氮唑化合物的合成研究进展
张发光, 彭星, 马军安
2019, 39(1): 109-116  doi: 10.6023/cjoc201808007
[摘要]  (271) [HTML全文] (271) [PDF 585KB] (271)
摘要:
三氟甲基取代的三氮唑及四氮唑化合物在药物、农药、催化及材料等领域发挥着越来越重要的作用,其合成方法也日益受到重视.对近10年来三氟甲基三氮唑及四氮唑化合物的合成方法研究进展进行了分类归纳总结,着重展示了三氟甲基炔烃、三氟乙酰基衍生物、三氟甲基吡喃酮及三氟重氮乙烷等含氟砌块在这两类杂环合成中的应用.
REVIEWS
Transition Metal-Catalyzed Regio-selective Aromatic C—H Bond Oxidation for C—O Bond Formation
Fanzhi Yang, Han Zhang, Xuri Liu, Bo Wang, Lutz Ackermann
2019, 39(1): 59-73  doi: 10.6023/cjoc201808017
[摘要]  (158) [HTML全文] (158) [PDF 823KB] (158)
摘要:
Recent years the great progress in transition metal-catalyzed direct aromatic C—H oxidation has been witnessed, which has been utilized in the preparation of various phenolic compounds. These transformations employ inter alia palladium, copper, ruthenium, iridium, etc. as the transition metal catalysts, and hypervalent iodine, persulfate, or oxygen as the oxidants. There have been several reviews in which the C—H oxidations with specific transition metal or oxidant was discussed. This review focuses specifically on transition metal-catalyzed aromatic C—H oxidations with ortho-, meta-, or para-selectivity, and rationalizes the possible generation mechanism of regio-selectivities, which might be controlled by the directing group via chelation-assistance, the ligand, or intrinsic properties of the substrate. The discussion section indicated the existing problems of transition metal-catalyzed aromatic C—H oxidations, as well as the possible limiting factors for the development and application of this strategy.
Progress on Trifluoroethylation Reactions Using Aryl(trifluoroethyl)iodonium Salts
Qiuyan Han, Chenglong Zhao, Chengpan Zhang
2019, 39(1): 84-94  doi: 10.6023/cjoc201808029
[摘要]  (111) [HTML全文] (111) [PDF 592KB] (111)
摘要:
Transition metal-free and metal-catalyzed reactions using aryl(trifluoroethyl)iodonium salts as the trifluoroethylation reagents are summarized in this review. A large number of different types of N-, O-, S-, and C-nucleophiles were readily trifluoroethylated in these reactions under mild conditions. The results revealed that aryl(trifluoroethyl)iodonium salts possess much higher electrophilic reactivity than the other CH2CF3 sources. Especially, aryl(trifluoroethyl)iodonium bis(trifluoromethanesulfonyl)amides are stable and slightly soluble in water, which were successfully applied in the aqueous trifluoroethylation of amino acid derivatives and peptides. The utilization of aryl(trifluoroethyl)iodonium salts for aromatic trifluoroethylation has promisingly solved the problems that arise from the other reagents. These achievements have also demonstrated the synthetic possibilities of direct trifluoroethylation using aryl(trifluoroethyl)iodonium salts under transition-metal catalysis.
研究论文
含氟咪唑啉型有机催化剂在不对称Aldol反应中的研究
解晓娟, 张忠, 赵华欣, 万文, 郝健
2019, 39(1): 117-121  doi: 10.6023/cjoc201809026
[摘要]  (150) [HTML全文] (150) [PDF 500KB] (150)
摘要:
手性1,2-二醇骨架是天然产物或生物活性分子构建过程中的重要骨架,而α-羟基酮参与的不对称Aldol缩合反应是实现手性1,2-二醇骨架的重要手段.设计并合成了含三氟甲基的咪唑啉型化合物,并将其应用于羟基丙酮和醛的不对称Aodol缩合反应.研究结果表明,当采用含氟咪唑啉(2R,4S)-4-苄基-1,2-二甲基-2-三氟甲基咪唑啉(1a)作为不对称Aldol反应的催化剂时,能够以产率高达96%、最高ee值达到99%及dr值达到15:1的效率高效构建一系列顺式1,2-二醇产物.同时,我们也初步探讨了氟-氢键在不对称催化反应中的作用.
PhI(OAc)2参与的β-酮酸酯及β-酮酰胺亲核氟化反应
吴文胜, 袁航, 黄高魁, 蒋春辉, 陆鸿飞
2019, 39(1): 137-143  doi: 10.6023/cjoc201808047
[摘要]  (110) [HTML全文] (110) [PDF 500KB] (110)
摘要:
报道了一种构建含氟的β-酮酸酯及β-酮酰胺的亲核氟化反应.该反应采用PhI(OAc)2为氧化剂、3HF·Et3N为氟化试剂,在室温下反应30 min高效构建一系列含有季碳中心的含氟化合物.与传统的亲电氟化反应相比,该方法具有无金属参与、反应时间短、反应条件简单、反应收率高等优点.
α-三氟甲基苄溴合成烷基硫酸盐——脱卤亚磺化反应的延伸
付晓林, 孙岩, 赵志刚, 郭勇, 陈庆云, 念保义
2019, 39(1): 144-150  doi: 10.6023/cjoc201810022
[摘要]  (125) [HTML全文] (125) [PDF 519KB] (125)
摘要:
脱卤亚磺化反应是引入氟烷基基团的一种常用方法.探索了α-三氟甲基苄溴在脱卤亚磺化条件下的反应,发现产物并不是亚磺酸盐[ArCH(CF3)SO2Na],而是烷基硫酸盐[ArCH(CF3)OSO3Na].即使在烯烃的存在的条件下,α-三氟甲基苄溴在脱卤亚磺化条件下产生了自由基,也不与烯烃发生加成反应,而是直接生成亚磺酸盐,亚磺酸盐被空气氧化成烷基硫酸盐.
环糊精/氨基粘土超分子水凝胶的构筑及其I3-/I2吸附性能
牛杰, 陈湧, 刘育
2019, 39(1): 151-156  doi: 10.6023/cjoc201807054
[摘要]  (143) [HTML全文] (143) [PDF 2276KB] (143)
摘要:
氨基粘土(Aminoclay,AC)是一种具有片层结构的硅酸盐材料,由于其在水中具有高分散性的特点,因此被广泛应用于构筑智能杂化水凝胶.利用静电相互作用,将带负电的7-[6-脱氧-6-(2-乙磺酸)]-β-环糊精(磺化环糊精,SCD)与氨基粘土非共价结合,构筑了一种新型的杂化水凝胶,并利用X射线衍射(XRD)、扫描式电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)、Zeta电势、流变测试等对所构筑的凝胶进行了结构表征.进而发现SCD-AC凝胶在水相中展现出对I3-离子的高效吸附特性,并且在有机相中能够吸附I2分子.
苯并二噻吩/苯并噻二唑ADA型光电化合物:氟取代的影响
梁龙, 刘丽娜, 陈学强, 项宣, 凌君, 鲁郑全, 李靖靖, 李维实
2019, 39(1): 157-169  doi: 10.6023/cjoc201808034
[摘要]  (128) [HTML全文] (128) [PDF 5961KB] (128)
摘要:
在其组成的共轭基元上进行氟取代是有机光电材料功能修饰的常见策略之一.在前期苯并二噻吩/苯并噻二唑ADA型小分子光电化合物基础上,在两个苯并噻二唑基元上引入不同个数的氟取代基,考察氟修饰位置和个数对其基本性质、场效应晶体管和光伏性能的影响.研究表明,随着氟原子数目的增加,化合物的溶解性能降低,热稳定性提高,最高占有轨道和最低空轨道能级降低,但光谱吸收范围变化不大.有机场效应晶体管器件测试表明,当苯并噻二唑单氟代且位于外侧位点时,化合物的空穴迁移率有所降低;当苯并噻二唑双氟代时,迁移率得到了明显提高,达到0.27 cm2·V-1·s-1.光伏器件研究发现,氟原子的引入提高了器件的开路电压,但活性层形貌变差,最终导致短路电流密度和电池效率下降.
全氟烷基次磺酸与炔烃和联烯的加成反应
李晓波, 赵娟, 刘倩, 蒋敏, 刘金涛
2019, 39(1): 183-191  doi: 10.6023/cjoc201808036
[摘要]  (130) [HTML全文] (130) [PDF 496KB] (130)
摘要:
研究了原位生成的全氟烷基次磺酸分别与炔烃和联烯的加成反应,成功合成了一系列全氟烷基烯基亚砜类化合物.结果显示芳基或烷基取代的炔烃与全氟烷基次磺酸在加热条件下可以直接得到符合马氏规则的加成产物,当炔烃上连有强吸电子取代基时,则生成类Michael加成产物.全氟烷基次磺酸与富电子联烯的加成反应选择性地发生在空间位阻较小的双键上,当联烯分子中含有吸电子基团时,则会优先选择与连接吸电子基团的双键进行反应.
全氟烷基取代的芴基炔膦酸二乙酯化合物的一锅法合成
孙小莉, 孙振华, 韩敏敏, 韩靖, 何伟民, 陈杰, 邓红梅, 邵敏, 张慧, 曹卫国
2019, 39(1): 192-199  doi: 10.6023/cjoc201808028
[摘要]  (100) [HTML全文] (100) [PDF 723KB] (100)
摘要:
报道了一种以茚酮、丙二腈、全氟烷基炔膦酸二乙酯为原料合成全氟烷基取代的芴基炔膦酸二乙酯类化合物的新方法.采用一锅合成法,可将不同基团取代的茚酮直接转化为一系列相应的全氟烷基取代的芴基炔膦酸二乙酯衍生物.整个反应过程无需金属催化,具备反应条件温和、区域选择性好、产率较高、操作简便等优点.
手性吡咯亚磷酰胺/Rh催化的1, 1-双取代烯烃的不对称氢甲酰化反应
贾肖飞, 任新意, 王正, 夏春谷, 丁奎岭
2019, 39(1): 207-214  doi: 10.6023/cjoc201809033
[摘要]  (109) [HTML全文] (109) [PDF 0KB] (109)
摘要:
发展了一类吡咯取代的手性亚磷酰胺配体,并将其成功地应用于铑催化的1,1-双取代烯烃的不对称氢甲酰化反应,以优秀的区域选择性、良好的化学选择性和对映选择性(71%~86%ee)得到相应的手性直链醛,反应的转化数(Turnover Number,TON)值最高达到8900.该类催化剂容易制备且具有广泛的官能团兼容性,通过不对称氢甲酰化反应为手性α-烷基-β-甲酰基丙酸酯类化合物的合成提供了一类新的方法.
通过苄醇与炔烃的环化反应快速高效构建茚及螺环茚
余佳佳, 杨珊, 吴镇, 朱晨
2019, 39(1): 223-231  doi: 10.6023/cjoc201808009
[摘要]  (119) [HTML全文] (119) [PDF 533KB] (119)
摘要:
作为一类重要的碳环化合物,茚、螺环茚及其衍生物常见于各种天然产物骨架结构中,并作为合成中间体广泛地应用于材料、医药、有机不对称合成等领域.在路易斯酸TiCl4或AlCl3作用下,二苯甲醇或芳基取代环醇等苄醇通过生成碳正离子中间体,与炔烃进行环化反应高效合成多种茚及螺环茚.该反应仅需30 min,反应过程中完成了2个新C—C键的构建,对具有各种取代基的炔烃均有较好的适用性.芳基取代的环丁醇、环己醇、环庚醇、环辛醇以及环十二醇都可以适用于该方法,多样性地构建多种有合成价值的螺环骨架.该方法具有操作简便、反应时间短、条件温和等优点.
苯乙烯的氧化三氟甲硫基化反应
王建勇, 马岚, 李彦, 王细胜
2019, 39(1): 232-237  doi: 10.6023/cjoc201807052
[摘要]  (130) [HTML全文] (130) [PDF 512KB] (130)
摘要:
使用稳定易得的三氟甲硫基银作为“三氟甲硫基”源,通过苯乙烯的三氟甲硫基化/氧化反应,合成了一系列多取代α-三氟甲硫基苯乙酮.以二甲基亚砜和氯仿的为溶剂,过硫酸钾为氧化剂,通过自由基历程进行双官能化反应,在温和条件下,以中等到良好的收率实现了一系列不同取代的苯乙烯的氧化三氟甲硫基化的高效转化,为α-三氟甲硫基苯乙酮的合成提供了一种简单、步骤经济的有效合成方法.
基于分子内交叉氧化偶联反应来非对映选择性构建全碳季碳中心
陈伟, 郭人予, 龚建贤, 杨震
2019, 39(1): 238-248  doi: 10.6023/cjoc201805023
[摘要]  (120) [HTML全文] (120) [PDF 1150KB] (120)
摘要:
立体位阻拥挤C—C键,尤其是包含全碳季碳中心C—C键的构建一直是现代有机合成化学的挑战.利用硝酸铈铵(CAN)诱导的双烯醇硅醚化合物分子内交叉氧化偶联反应来非对映选择性地构建连续全碳季碳中心以及叔碳中心.该方法在相对温和的反应条件下,以CAN作为单电子氧化剂,高产率、高非对映选择性地构建立体位阻拥挤的C—C键.本研究提供了一种通过分子内交叉氧化偶联反应来实现两个不同片段高效连接的有效手段,可以应用到复杂天然产物的全合成研究中去.
镍催化的偕二氟芳基乙烯与有机锌交叉偶联反应立体选择性合成(Z)-单氟烯烃
张娟, 王碧云, 刘熠森, 曹松
2019, 39(1): 249-256  doi: 10.6023/cjoc201807013
[摘要]  (136) [HTML全文] (136) [PDF 547KB] (136)
摘要:
报道了在NiCl2(dppp)催化和氯化锂促进下,室温下将偕二氟芳基乙烯与有机锌试剂进行交叉偶联反应,合成一系列(Z)-单氟烯烃的方法.该方法具有反应条件温和、操作简单、官能团兼容性较好、立体选择性出色等优点.
ARTICLE
Palladium-Catalyzed Intramolecular Fluoroarylation of Alkenes
Wencheng Yang, Xiaoxu Qi, Pinhong Chen, Guosheng Liu
2019, 39(1): 122-128  doi: 10.6023/cjoc201810026
[摘要]  (138) [HTML全文] (138) [PDF 488KB] (138)
摘要:
A novel palladium-catalyzed intramolecular fluoroarylation of alkenes has been developed, in which ArIF2 was employed as fluorine source as well as Ⅰ(Ⅲ) reagent to activate olefin, to deliver the fluoroarylation products from 4-aryl- 1-olefins in moderate to good yields. The current transformation presents a convenient method to provide fluorotetralins and fluorochromanes under mild conditions from alkenes tethered arenes.
Iron(Ⅲ) Porphyrin Catalyzed Cyclization of Ketones with Dimethyl Sulfoxide and Ammonium Acetate: One-Pot Synthesis of Pyridines
Yufeng Liu, Zhongzhong Cao, Miaodong Su, Hui Li, Meiqiang Fu, Qiang Liu, Weiping Luo, Cancheng Guo
2019, 39(1): 129-136  doi: 10.6023/cjoc201809014
[摘要]  (121) [HTML全文] (121) [PDF 486KB] (121)
摘要:
An iron(Ⅲ)-porphyrin-catalyzed cyclization of ketones with dimethyl sulfoxide (DMSO) and ammonium acetate for the synthesis of unsymmetrical and symmetrical pyridines by employing DMSO as C4 or C6 source has been developed. Various aryl ketone derivatives react readily with DMSO, producing the pyridines in yields of 30%~85%. This method uses non-noble metals and proceeds under mild reaction conditions with operational simplicity, which thus allows the expedient assembly of pyridines from readily available ketones. Based on the preliminary experiments, a plausible mechanism of this transformation is disclosed.
Molecular Design and Property Prediction for a Series of 3, 3-Bis(difluoroamino)-1, 5-substituted-pentane Derivatized as Energetic Plasticizers
Wanjun Wang, Huan Li, Renming Pan, Weihua Zhu
2019, 39(1): 170-176  doi: 10.6023/cjoc201808024
[摘要]  (118) [HTML全文] (118) [PDF 802KB] (118)
摘要:
3, 3-Bis(difluoroamino)-1, 5-dinitratopentane was used as energetic plasticizer with improving energy properties and low glass transition temperature. To obtain more new difluoroamino energetic compounds with similar sturctures, a series of 3, 3-bis(difluoroamino)-1, 5-substituted-pentane derivatives were designed as candidates of novel energetic plasticizers. The heats of formation (HOFs), electronic structure, energy property and thermal stability were studied using density functional theory (DFT) method. The difluoroamino groups can increase energy gaps of electronic structure, density and detonation properties among the title compounds. Especially, 1, 3, 3, 5-tetra(difluoroamino)pentane (S3) has given outstanding values of potential energetic plasticizer. Its crystal density (1.91 g/cm3), detonation velocity (9.01 km/s), detonation pressure (37.31 GPa) and impact sensitivity (h50 29.83 cm) are very close to those of cyclotetramethylenetetranitramine (HMX). Furthermore, S3 can be synthesized via some mature processes in five steps.
ARTICLES
Copper-Catalyzed Hydroxytrifluoromethylthiolation of Arylpropynones
Juanjuan Hu, Yangen Huang, Xiuhua Xu, Fengling Qing
2019, 39(1): 177-182  doi: 10.6023/cjoc201808041
[摘要]  (127) [HTML全文] (127) [PDF 451KB] (127)
摘要:
Recently, the preparation of fluorinated compounds through difunctionalization strategies has become a hot research area in fluorine chemistry. In this work, a copper-catalyzed hydroxytrifluoromethylthiolation of arylpropynones for the synthesis of the corresponding trifluoromethylthiolated enols was developed. The copper salt and solvent are crucial to the yields of this reaction. Under optimized reaction conditions, a series of trifluoromethylthiolated enols were obtained in moderate to good yields.
Visible-Light Promoted Preparation of Trifluoromethylated Tetrahydrofuran and Tetrahydropyran
Na Wang, Qiang-Shuai Gu, Yong-Feng Cheng, Lei Li, Zhong-Liang Li, Zhen Guo, Xin-Yuan Liu
2019, 39(1): 200-206  doi: 10.6023/cjoc201808048
[摘要]  (133) [HTML全文] (133) [PDF 474KB] (133)
摘要:
An efficient protocol for facile access to trifluoromethylated tetrahydrofuran and tetrahydropyran has been developed under visible light irradiation conditions via radical 1, 2-alkoxyl-trifluoromethylation of unactivated alkene. It features the use of readily commercially available and operatively simple trifluoromethanesulfonyl chloride as a trifluoro- methyl radical source, thus making the protocol potentially appealing for practical preparation.
Nickel-Catalyzed Difluoromethylation of (Hetero)aryl Bromides with BrCF2H
Xing Gao, Xu He, Xingang Zhang
2019, 39(1): 215-222  doi: 10.6023/cjoc201808014
[摘要]  (146) [HTML全文] (146) [PDF 489KB] (146)
摘要:
A nickel-catalyzed direct difluoromethylation of (hetero)aryl bromides with bromodifluoromethane (BrCF2H) is described. This reaction features high efficiency, broad substrate scope and high functional group tolerance, providing a cost-efficient and straightforward route for applications in medicinal chemistry. Preliminary mechanistic studies reveal that a nickel-based, reductive cross-coupling catalytic cycle is involved in the reaction.
Pentafluoroethyl-Substituted Sulfonium Ylides: New Electrophilic Pentafluoroethylating Reagents
Yafei Liu, Hangming Ge, Long Lu, Qilong Shen
2019, 39(1): 257-264  doi: 10.6023/cjoc201807018
[摘要]  (97) [HTML全文] (97) [PDF 460KB] (97)
摘要:
Two electrophilic pentafluoroethylating reagents of pentafluoroethyl(p-methylphenyl)sulfonium bis(carbometh- oxy)methylide (4a) and pentafluoroethyl(4-nitrophenyl)sulfonium bis(carbomethoxy)methylide (4b), and their reactions under mild conditions with β-ketoesters, aryl iodides and heteroaromatics are described.
ZnO-Promoted Wittig gem-Difluoroolefination of Aldehydes with [Ph3P+CF2H·Br-]
Jiao Yu, Jinhong Lin, Jichang Xiao
2019, 39(1): 265-269  doi: 10.6023/cjoc201806024
[摘要]  (124) [HTML全文] (124) [PDF 638KB] (124)
摘要:
Wittig gem-difluoroolefination of aldehydes with difluoromethyl phosphonium salt (Ph3P+CF2H·Br-) by using zinc oxide as a base is described. Although the proton in the CF2H group is acidic and a base could easily lead to its deprotonation to form ylide (Ph3P+CF2-), the attack of the base at the positive phosphorus atom may also take place to produce a nucleophilic [HCF2-] equivalent, and then nucleophilic difluoromethylation instead of Wittig reaction would occur. The use of ZnO as the base favored the Wittig reaction and the nucleophilic difluoromethylation was not observed. Furthermore, the excessive ZnO and Zn salts produced from ZnO could be easily removed by filtration, which may be convenient for the purification process.
研究简报
邻三氟甲磺酸酯基取代二芳基碘盐的合成及其抑菌活性研究
崔丽媛, 陈煌冠, 马静怡, 韩建伟, 王利民
2019, 39(1): 270-276  doi: 10.6023/cjoc201808043
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摘要:
二芳基碘盐具有潜在的生物活性.合成了13种邻位三氟甲磺酸酯基取代的线性二芳基碘盐,利用核磁共振谱和质谱表征了它们的结构.通过微量肉汤稀释法测试该系列化合物的最低抑菌浓度(MIC),结果表明含氟基团取代的二芳基碘盐对于大肠杆菌(E.coli)、金黄色葡萄球菌(S.aureus)和枯草芽孢杆菌(B.subtilis)具有良好的抑菌性.其中,化合物(3-氟苯基)(2-(((三氟甲基)磺酰基)氧基)苯基)三氟甲磺酸碘盐(1)对大肠杆菌、金黄色葡萄球菌和枯草芽孢杆菌的MIC值分别为16,4,4 μg·mL-1,明显低于市售抗菌剂卡松(异噻唑啉酮).此外,扫描电子显微镜(SEM)结果显示,该二芳基碘盐能够明显诱导细菌死亡;细胞试验结果显示在体外条件下,化合物1与市售卡松对Hela细胞的生长影响相当,是一种低毒性的抗菌剂.
亮点介绍
亮点介绍(8)篇
2019, 39(1): 277-280
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摘要: