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综述与进展
重氮化合物参与的连续流动反应
郜云鹏, 王剑波
2018, 38(6): 1275-1291  doi: 10.6023/cjoc201712029
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摘要:
重氮化合物是一种用途广泛的有机砌块,能够作为1,3-偶极子、亲核试剂以及卡宾前体参与到各种有机分子的构建之中.但重氮化合物潜在的毒性、不稳定性以及爆炸风险限制了它的应用潜力.连续流动技术在这一领域的应用能够有效保证反应的安全性,并为重氮化合物的大批量应用提供了可能.按照重氮化合物的种类分类,系统地归纳了近年来连续流动技术在重氮化合物参与的各种转化中的应用.
“受阻路易斯酸碱对”活化小分子反应研究进展
张震北, 孙伟, 曹治珊
2018, 38(6): 1292-1318  doi: 10.6023/cjoc201801003
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摘要:
“受阻路易斯酸碱对(FLP)”是最近十几年提出的一个崭新的化学理论.由于其独特的化学特性,受阻路易斯酸碱对在非金属催化体系中占据了一席重要的位置.受阻路易斯酸碱对具有活化小分子的特征,包括氢气、烯烃、炔烃、二氧化碳、环醚、硅烷等在内的小分子都可以利用受阻路易斯酸碱对体系进行活化,这为发展主族元素参与的催化反应打开了新思路.综述了受阻路易斯酸碱对的结构和反应特征,并介绍了近年来关于受阻路易斯酸碱对催化活化小分子的反应.
金属催化不饱和烃的官能化应用于吡咯烷和吡咯啉类化合物的合成
张金刚, 吴正兴, 谢芳, 张万斌
2018, 38(6): 1319-1326  doi: 10.6023/cjoc201802001
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摘要:
吡咯烷和吡咯啉作为重要的结构单元在医药、农药、材料等领域中具有广泛应用,多年来许多关于此类结构的合成方法被广泛报道.近年来,伴随金属有机化学的快速发展,金属催化不饱和烃的官能化反应具有高效性和多样性等优点,逐渐成为有机合成方法学的研究热点.因此通过金属催化不饱和烃的官能化反应构建吡咯烷和吡咯啉结构具有重要的意义.概述了各种金属催化的不同类型不饱和烃的官能化反应合成吡咯烷和吡咯啉类化合物的进展.
邻碳硼烷与不饱和化合物环加成反应的实验和理论研究进展
母伟花, 程瑞姣, 尚英伟, 贺仁泽, 李冬丽, 傅冕
2018, 38(6): 1327-1340  doi: 10.6023/cjoc201712044
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摘要:
邻碳硼烷及其所衍生的邻碳硼炔化合物能够与多种不饱和化合物发生环加成反应转化为结构新颖的功能碳硼烷衍生物.这些功能碳硼烷衍生物在硼中子捕获疗法、催化合成、药物设计等诸多领域都有着广阔的应用前景.近年来,人们在邻碳硼烷和邻碳硼炔的官能化领域取得了显著成就,尤其在反应条件优化、反应选择性控制、反应机理研究等方面取得了明显进步.对近十年以来国内外课题组在邻碳硼烷与炔烃、烯烃、多环或杂环芳烃等不饱和化合物的环加成反应领域所取得的实验研究成果进行了总结,并对邻碳硼炔参与的[2+2+2]、[2+2+1]、[2+2]、[3+2]、[4+2]、[5+2]等环加成反应的实验和理论研究成果、尤其是反应机理作了详细介绍,最后对该领域的发展前景进行了展望.
过渡金属催化的成胍反应高效构建胍类衍生物
王连军, 迟樾, 张文雄, 席振峰
2018, 38(6): 1341-1349  doi: 10.6023/cjoc201801037
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摘要:
胍及其衍生物是一类很重要的含氮有机化合物,在医药、工农业中应用非常广泛.胍类化合物的合成最先通过各种胍基化试剂制得,近年来逐渐转向由胺与碳二亚胺经合适的催化剂直接制备成胍.系统综述了近十多年过渡金属催化胺与碳二亚胺的成胍反应直接构建非环胍和环状胍的催化机理、反应体系、底物范围及成胍产物的结构特点等.
胺-胺氧化偶联合成亚胺的研究进展
刘迪, 张成慧, 韩楠, 杜萌萌, 张效露, 赵朋杉, 杨萍
2018, 38(6): 1350-1363  doi: 10.6023/cjoc201801017
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摘要:
亚胺是一类性质活泼的中间体且具有很好的抗菌作用,因而受到广泛关注.胺-胺氧化偶联合成亚胺的路线由于具有原子经济性高和对环境友好等优点,已成为研究的热点.主要从催化剂及其催化机理两方面对胺-胺氧化偶联合成亚胺的研究进展进行综述.分别对贵金属、非贵金属、光催化、仿生催化以及聚苯胺、氧化石墨、偶氮二异丁腈等体系催化的胺-胺氧化偶联合成亚胺反应进行了详细地介绍,重点论述了各种催化剂的催化性能、优缺点和底物适用范围,还对主要催化体系的催化机理作了分析.需要指出,尽管目前胺-胺氧化偶联合成亚胺的催化剂研究已有了较大的发展,但在一定程度上依然存在着催化剂成本高,反应条件苛刻,对胺-胺交叉氧化偶联反应的催化性能较低,以及需要使用特定氧化剂、碱性助剂和溶剂等缺点.最后,基于胺-胺氧化偶联合成亚胺路线存在的问题,指出了该领域的研究方向.
1, 8-萘酰亚胺类荧光探针在双光子成像中应用的研究进展
谢振达, 付曼琳, 尹彪, 朱勍
2018, 38(6): 1364-1376  doi: 10.6023/cjoc201712031
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摘要:
荧光成像技术由于其灵敏度高、操作简单、可实时动态进行细胞、组织以及生物活体成像而受到极大关注,相对于单光子荧光成像技术,双光子成像技术具有高分辨率、强组织穿透性以及低的组织自发荧光干扰等显著的优越性.1,8-萘酰亚胺作为典型的电子供体-π-电子受体(D-π-A)双光子荧光染料,具有光稳定性、大斯托克斯/反斯托克斯位移等优点被广泛应用于酶、活性碳簇、活性氧簇、活性氮簇、生物硫醇、离子等的双光子成像中.依据1,8-萘酰亚胺类荧光探针发光机制,即分子内电荷转移、光诱导电子转移、荧光共振能量转移等发光机制,综述1,8-萘酰亚胺近些年来在双光子成像领域中的应用,并展望了其未来的发展趋势.
聚集体中的三重态-三重态湮灭上转换
范春英, 伍晚花, 杨成
2018, 38(6): 1377-1393  doi: 10.6023/cjoc201712034
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摘要:
三重态-三重态湮灭(TTA)上转换是一项将低能量的光转换成高能量光的技术,具有所需激发光强度低、光敏剂吸光能力强、工作波长可调、量子效率高等优点,因其在太阳能电池、生物成像、光催化及光电器件等方面的潜在应用价值而受到广泛关注.由于TTA上转换的两个重要过程——三重态光敏剂向受体的能量传递(TTET)与受体分子间发生三重态湮灭(TTA)均属于Dexter机制,需要通过碰撞来完成,因而目前TTA上转换多数在低粘度、除氧的有机溶剂中完成,这在一定程度上限制了它的实际应用.近年来,探索能够隔绝空气、分子扩散受限体系中特别是固相中的高效上转换受到研究者的广泛关注.介绍了TTA上转换发光机理,详细综述了TTA上转换在包括高分子聚合物、固态晶体、超分子凝胶、超分子自组装体以及纳米颗粒等聚集体中的研究进展.
研究论文
增强型超分子荧光探针对拉帕替尼的识别及其在细胞成像中的应用
王成会, 唐青, 席芸芸, 杨梅, 李涛, 黄英, 陶朱
2018, 38(6): 1394-1400  doi: 10.6023/cjoc201711018
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摘要:
通过超分子识别设计了八元瓜环与派洛宁Y超分子荧光探针2PyY@Q[8],研究了该探针对抗癌药物拉帕替尼的识别性质.研究结果表明,该探针在水溶液中对拉帕替尼具有良好的识别能力及选择性,在一定浓度范围内其线性关系良好,其检出限为1.44×10-8 mol/L.细胞成像结果显示该探针在前列腺癌细胞中对拉帕替尼具有很好的响应,可用于生物细胞内拉帕替尼的识别检测.
二苯氨基硫脲类索拉菲尼衍生物的合成及抗肿瘤活性评价
管道坤, 孙少峰, 陈静, 何作鹏, 孔祥凯, 王宁宁, 姚建文, 王洪波
2018, 38(6): 1414-1421  doi: 10.6023/cjoc201802005
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摘要:
以2-吡啶甲酸和取代苯胺为原料,设计合成了17个新型二苯氨基硫脲类索拉菲尼衍生物.目标化合物均经过NMR和HRMS进行结构表征.采用人结肠癌细胞HCT116、人乳腺癌细胞MDA-MB-231、人前列腺癌细胞PC-3和小鼠黑色素瘤细胞B16BL6对目标化合物的体外抗肿瘤活性进行了研究.结果表明1-(4-氯-3-三氟甲基苯基)-3-{4-[2-(异丙氨甲酰基)吡啶-4-氨基]苯基}硫脲(9g)对四种细胞株的抑制活性均优于阳性药物索拉菲尼,1-(3-三氟甲基-4-氯苯基)-3-{4-[2-(甲基氨甲酰基)吡啶-4-氨基]苯基}硫脲(9b)和1-(3-三氟甲基-4-氟苯基)-3-{4-[2-(异丙氨甲酰基)吡啶-4-氨基]苯基}硫脲(9j)对MDA-MB-231细胞株、PC-3细胞株和B16BL6细胞株具有优于索拉菲尼的抑制活性,同时探讨了新化合物9j与B-Raf受体的三维晶体结构(5HI2)活性位点的结合模式,为今后新型索拉菲尼衍生物的设计合成提供了有用参考.
不对称合成手性3, 5-二取代脯氨酸及其衍生物
赵亮, 周圣斌, 童军华, 王江, 柳红
2018, 38(6): 1437-1446  doi: 10.6023/cjoc201712005
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摘要:
选用甘氨酸等当体镍螯合物与αβ-不饱和酮进行不对称Michael加成反应,在室温条件下,以1,8-二氮杂二环十一碳-7-烯(DBU)为碱,甲醇为溶剂,不对称合成了3,5-二取代脯氨酸及其衍生物.该方法具有操作简单、收率高、底物适用范围广的特点,为3,5-二取代脯氨酸及其衍生物的不对称合成提供了新的研究思路.
2-吗啉基-1-丙基-1H-吲哚-3-取代酰腙类化合物的合成及抑菌活性
巫受群, 李小琴, 孟娇, 甘宜远, 田坤, 王贞超, 欧阳贵平
2018, 38(6): 1447-1453  doi: 10.6023/cjoc201712030
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摘要:
以2-吲哚酮为先导化合物,设计合成一系列2-吗啉基-1-丙基-1H-吲哚-3-取代酰腙类化合物.目标化合物结构经核磁共振波谱(1H NMR和13C NMR)和高分辨质谱仪(HRMS)进行确证.采用浊度法测试了目标化合物的离体抑菌活性,抑菌活性测试结果表明:目标化合物对柑橘溃疡病菌(Xanthomonas axonopodis pv.CitriX.citri)、烟草青枯病菌(Ralstonia.SolanacearumR.solanacearum)和水稻白叶枯病菌(Xanthomonas oryzae pv.OryzaeX.oryzae)均表现出一定的抑制活性.化合物2-氰基-N'-((2-吗啉基-1-丙基-1H-吲哚-3-基)亚甲基)乙酰肼(12a)、4-氯-N'-((2-吗啉基-1-丙基-1H-吲哚-3-基)亚甲基)苯甲酰肼(12c)、4-氟-N'-((2-吗啉基-1-丙基-1H-吲哚-3-基)亚甲基)苯甲酰肼(12f)、N'-((2-吗啉基-1-丙基-1H-吲哚-3-基)亚甲基)-4-硝基苯甲酰肼(12k)和N'-((2-吗啉基-1-丙基-1H-吲哚-3-基)亚甲基)异烟肼(12m)表现出较好的抑制活性;化合物12a12c12f12k12m对水稻白叶枯病菌的EC50为73.79、61.94、59.70、36.72和82.79 μg/mL,抑制活性优于对照药叶枯唑和噻菌铜(EC50分别为92.4、120.22 μg/mL).
三氯异氰尿酸作为氯源实现α-氰基酮和1, 3-二羰基类化合物的氯化
苏瀛鹏, 石娅, 常兵兵, 吴丽丽, 种思颖, 张为钢, 黄丹凤, 王克虎, 胡雨来
2018, 38(6): 1454-1461  doi: 10.6023/cjoc201712042
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摘要:
报道了以三氯异氰尿酸作为氯源,在室温条件下高效实现了α-氰基酮类化合物和1,3-二羰基类化合物氯化反应的研究.该反应过程条件温和,无需额外添加氧化剂或碱.
两种七元瓜环与3-(2-萘基)-丙氨酸的包结行为分析
白东, 周杨, 卢季红, 刘青云, 陈青, 陶朱, 肖昕
2018, 38(6): 1477-1483  doi: 10.6023/cjoc201801020
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以反式七元瓜环(iQ[7])和七元瓜环(Q[7])作为主体分子,一对氨基酸对映体L-3-(2-萘基)-丙氨酸(L-NA)及D-3-(2-萘基)-丙氨酸(D-NA)为客体分子,利用紫外-可见吸收光谱、荧光光谱、等温滴定量热分析、基质辅助激光解吸电离飞行时间质谱以及核磁共振技术等手段,对比探究了这两种具有不同空腔大小的七元瓜环与这一对氨基酸对映体之间的自组装模式的异同点,实验结果表明:这四组主客体包结物具有相同的作用模式,均为瓜环的空腔包结了客体分子的萘环部分而客体分子的氨基及羧酸部分位于瓜环的端口外侧,主客体均以1:1的作用比相互配位形成较为稳定的超分子自组装体,同时发现两种七元瓜环对L/D-NA手性对映体的分子选择性略有不同.
某些A-homo甾体内酰胺噻唑衍生物的合成及抗肿瘤活性评估
黄燕敏, 庞春玲, 杨春晖, 展军颜, 甘春芳, 庞丽萍, 刘晓兰, 崔建国
2018, 38(6): 1484-1492  doi: 10.6023/cjoc201710005
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从睾酮出发,经过3-羰基肟化、Beckmann重排反应构建A-环甾体内酰胺甾核骨架,并以此为母体对17-羟基进行官能团改造与结构修饰,引入一些杂环基团,合成了一些结构新颖的A-Homo甾体内酰胺噻唑衍生物.通过IR、NMR及HRMS等现代分析方法对化合物进行了结构表征,并对化合物进行体外抑制肿瘤细胞生长增殖活性测试,结果表明其中某些化合物对所测试肿瘤细胞具有明显的抑制活性,但对人正常肾上皮细胞没有明显的抑制作用.
偶氮桥联的1, 3, 5-多取代三唑类化合物的合成及抑菌活性
李长胜, 邹玉龙, 贾长青, 覃兆海, 马永强
2018, 38(6): 1500-1506  doi: 10.6023/cjoc201710011
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以1,3,5-三取代-1,2,4-三唑类化合物为原料,在KMnO4或二氯异氰尿酸钠(SDCI)作用下,发生自身氧化偶联反应,合成了16个未见文献报道的偶氮桥联的1,3,5-多取代三唑类化合物.产物结构经1H NMR、13C NMR、IR、HRMS及X射线单晶衍射得以证实,并采用生长速率法对所有化合物进行了离体抑菌活性测试.结果表明:在浓度为50 μg/mL时,大部分化合物对所选六种病菌具有一定的抑制活性,其中1,1'-二正丁基-3,3'-二(2''-氯苯基)-5,5'-偶氮二(1,2,4-三唑)(3h)、1,1'-二丙基-3,3'-二(4''-氯苯基)-5,5'-偶氮二(1,2,4-三唑)(3k)对瓜果腐霉菌的抑制率接近三唑酮,而1,1'-二丙基-3,3'-二(2''-氯苯基)-5,5'-偶氮二(1,2,4-三唑)(3g)的抑制率要高于三唑酮.该类化合物反应操作简单、条件温和,对新农药创制及合成具有借鉴意义.
二萘并呋喃衍生物的合成及其抗肿瘤活性研究
宋永彬, 李丹, 杨异卉, 纪红蕊, 刘波
2018, 38(6): 1516-1524  doi: 10.6023/cjoc201712018
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摘要:
为了研究二萘并呋喃衍生物的构效关系,设计合成了两个系列的二萘[2,1-b:1',2'-d]呋喃衍生物,通过1H NMR、13C NMR、HRMS和IR数据对所有目标化合物进行了结构鉴定.通过噻唑蓝(MTT)法测试了目标化合物的体外抗肿瘤活性,大多数化合物对人肝癌细胞(HepG2和SMMC-7721)、人宫颈癌细胞(HeLa细胞)和急性早幼粒细胞白血病细胞(NB4细胞)显示了较强的抗肿瘤活性.其中N3N11-二羟基二萘并[2,1-b:1',2'-d]呋喃-3,11-二甲酰胺(13k)对SMMC-7721细胞显示了很强抑制作用,其半数抑制浓度为0.57 μmol·L-1,远低于阳性对照药5-氟脲嘧定的20.21 μmol·L-1.
ARTICLE
Aggregation-Induced Emission-Active Fluorescent Probe for Zn2+ Based on Isolongifolanone and Its Application in Plant-Cell Imaging
Zhonglong Wang, Jinlai Yang, Yiqin Yang, Xu Xu, Mingxin Li, Yan Zhang, Hua Fang, Haijun Xu, Shifa Wang
2018, 38(6): 1401-1413  doi: 10.6023/cjoc201712009
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摘要:
A series of hexahydroquinazolin-2-amine-based derivatives have been designed and synthesized from renewable isolongifolanone. Their solid states exhibited an enhanced emission and a dark green to bright yellow color range. In addition to good thermal stability, their solid-state fluorescence is not readily restricted by multiple conventional factors such as long term UV irradiation, increasing operated pressure and elevated heating temperature. In contrast to the derivatives which undergo serious aggregation-caused quenching (ACQ), the dimethylamino-substituted derivative 1-6, 6, 10, 10-tetramethyl-4-(4'-(N, N-dimethylamino)phenyl)-5, 7, 8, 9, 10, 10a-hexahydro-6H-6a, 9-methanobenzo[h]quinazolin-2-imino)methyl)naphthalen-2-ol (3e) demonstrate obvious aggregation-induced emission (AIE) characteristics. Moreover, these fluorescent derivatives were also used for specific and sensitive sensing of Zn2+ ion in aqueous solutions. Then, their photophysical mechanisms were obtained by the density functional theory calculations. These probes were successfully applied to image Zn2+ ion in pollen grains of Althaea rosea.
E-Z Isomerization of 1, 5-Bromotrichloromethylation Reaction Products and Trisubstituted Styrenes
Jin Li, Jingzhi Chen, Wenhao Huang, Xu Cheng
2018, 38(6): 1507-1515  doi: 10.6023/cjoc201712002
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摘要:
1, 5-Bromotrichloromethylation of α-cyclopropylstyrenes via a radical chain pathway was achieved with Ir[dF(CF3)ppy]2(dtbbpy)PF6 as a photoinitiator under visible-light irradiation to give trisubstituted styrenes with Z/E ratio of 30:70. When the reaction mixture was further irradiated, the Z/E ratio could be reversed and increased to 99:1, probably via an energy-transfer pathway involving the Ir photocatalyst. This visible-light-induced catalytic isomerization protocol could also be applied to trisubstituted styrenes to obtain products with Z/E ratios up to 99:1.
ARTICLES
Facile Microwave-Assisted Synthesis of 6, 7-Dihydro-5H-cyclopenta [4, 5]thieno [2, 3-d]pyrimidin-4-amine
Chaoyang Zong, Lijie Zhang, Mengting Gu, Yaquan Sun
2018, 38(6): 1422-1430  doi: 10.6023/cjoc201801009
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摘要:
25 kinds of 6, 7-dihydro-5H-cyclopenta[4, 5]thieno[2, 3-d]pyrimidin-4-amines were synthesized. Under microwave irradiation conditions, cyclopentanone, malononitrile and elemental sulfur reacted in ethanol to form 2-amino-5, 6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (1). Compound 1 reacted with N, N-dimethylformamide dimethyl acetal to give N-(3-cyano-5, 6-dihydro-4H-cyclopenta[b]-thien-2-yl)-N, N-dimethylmethanimidamide (2) under microwave irradiation conditions. Treatment of the compound 2 with aromatic amine under microwave irradiation yielded the corresponding compounds 6, 7-dihydro-5H-cyclopenta[4, 5]thieno[2, 3-d]pyrimidin-4-amine with good yields. The structures of the 25 target compounds were confirmed by melting point, NMR, IR and HRMS techniques.
Amidation of Acid Chlorides to Primary Amides with Ammonium Salts
Zhejian Li, Bao Gao, Hanmin Huang
2018, 38(6): 1431-1436  doi: 10.6023/cjoc201801034
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摘要:
A practical amidation reaction for the synthesis of primary amides is presented, in which the simple NH4Cl was identified as a practical and convenient amine source. A series of aromatic and aliphatic acid chlorides were successfully compatible with this protocol, affording the corresponding amides in good to excellent yields, which provides a rapid and reliable approach to amides from simple starting materials. Introducing the appropriate N-methyl pyrrolidone (NMP) into the system as solvent and acid-binding reagent plays a key role to avoid the use of stoichiometric amounts of base.
Synthesis and Fluorescent Property of Benzo [c]coumarin Carboxylic Derivatives
Juan Shi, Zunting Zhang
2018, 38(6): 1462-1468  doi: 10.6023/cjoc201712011
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摘要:
Two fluorescent compounds, 7-hydroxy-6-oxo-6H-benzo[c]chromene-8-carboxylic acid (3a) and 2, 3-benzo[f]-7-hydroxy-6-oxo-6H-benzo[c]chromene-8-carboxylic acid (3b) have been synthesized and characterized by the method of X-ray single crystal diffraction. 3a and 3b show high fluorescence quantum efficiency in both ethanol solution and solid state. In the crystal-state, dimerization of carboxylic group and intermolecular interaction lead to 3a owned a high fluorescence quantum efficiency (ФF=0.32). The dimers existing in 3a crystal lattice, are composed of carboxylic acid groups and have strong intermolecular interactions (bond lengths are 0.1870 nm, bond angles are 166.8°). All the atoms in dimer are nearly coplanar, showing extremely strong plane rigidity. The dimers are connected by C-H…O intermolecular hydrogen bonds, and the edge-to-face stackings exist in neighbor dimers.
A Facile Synthesis of CF3-Substituted Pyrazolidines and Pyrazolines
Lili Liu, Danfeng Huang, Yuxiang Wang, Lan Wen, Zheng Yang, Yingpeng Su, Kehu Wang, Yulai Hu
2018, 38(6): 1469-1476  doi: 10.6023/cjoc201712036
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摘要:
A Lewis acid-catalyzed[3+2] cycloaddition of trifluoromethylated N-acylhydrazones with alkenes was explored, and a series of CF3-substituted pryazolidines were obtained in high yields (up to 91%). The reaction features the use of cheap and readily available trifluoromethylated N-acylhydrazones as trifluoromethyl building blocks, mild reaction conditions and easy operation. Furthermore, the cycloadducts can be transformed into trifluoromethylated pyrazolines in excellent yields.
Application of Benzylic C-H Fluorination for the Formal Synthesis of syn-α, β-Difluoro-γ-amino Acid
Qingquan Liu, Xiangguo Hu
2018, 38(6): 1525-1529  doi: 10.6023/cjoc201712020
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摘要:
Benzylic C-H fluorination has emerged as a valuable tool for the introduction of fluorine. However, the powerfulness of benzylic C-H fluorination has not been tested in any multi-step synthesis. α, β-Difluoro-γ-amino acids are useful entities for biological application owing to the so-called fluorine conformational effect. In this work, benzylic C-H fluorination has been successfully utilized as the key step for the formal synthesis of syn-α, β-difluoro-γ-amino acid 1, a very challenging but useful target. The approach developed in this work could be viewed as more practical compared to the previous one, because:(1) no corrosive and toxic nucleophilic fluorinating reagents are used, (2) the overall yield is 18% (the previous approach is about 5%), and (3) the key benzylic C-H reaction developed by Chen and co-workers was scaled up to one gram without decreasing its original efficiency. A striking fluorine effect was observed:a carbon with one fluorine atom on the adjacent carbon is much less reactive than an ordinary carbon for the benzylic C-H fluorination.
Synthesis of 3-Acyl and 2-Acyl Imidazo [1, 2-a]pyridines by I2-Mediated Diamination of α, β-Unsaturated Ketones with 2-Aminopyridines
Wenquan Yu, Lina Song, Xianhai Tian, Ting Zhao, Manman Wang, Jie Wu, Yan Qiao, Junbiao Chang
2018, 38(6): 1530-1537  doi: 10.6023/cjoc201712045
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摘要:
Employing molecular iodine as the sole oxidant, a new and transition metal-free diamination reaction of α, β-unsaturated ketones with 2-aminopyridines has been developed. It can not only produce 3-acyl imidazo[1, 2-a]pyridines but can also generate novel 2-acyl derivatives regioselectively by changing the solvent and substituents in the 2-aminopyridine substrates.
CONTENT
Stereoselective Vinylation under Mild Metal-Free Conditions to Synthesize N-Vinylazoles
Shuang Li, Heng Xiang, Ruihang Jiang, Jia Ju, Pengchong Jiao, Hualei Yuan, Hongbin Sun, Huaqiang Cai
2018, 38(6): 1493-1499  doi: 10.6023/cjoc201710009
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摘要:
A metal-free synthetic protocol for N-vinylazoles has been developed. Twenty-two structurally diversed N-vinylazoles including 15 new compounds are obtained with good to high yield at near room temperature, and all of products consist trans-alkene moieties with high stereoselectivity.
研究简报
金属镍催化炔基铝与炔溴高效合成对称1, 3-二炔化合物
张刚, 杓学蓓, 李清寒, 杨学军
2018, 38(6): 1538-1543  doi: 10.6023/cjoc201802019
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摘要:
1,3-二炔类化合物是一类重要的有机合成中间体,被广泛应用于药物化学、有机合成及材料科学中.在室温条件下,以乙二醇二甲醚(DME)为溶剂,炔基溴(1 mmol)与炔基铝试剂(1.5 mmol)在Ni(acac)2(5 mol%)/DPPE(10 mol%)催化下进行偶联反应,以中等至优秀的收率得到了多种1,3-二炔烃类化合物.该反应体系对于带不同种类的功能基团的芳炔基铝试剂及炔基溴均有很好的催化活性.而且对于大位阻的α-萘炔及杂环2-噻吩炔也有较好的催化效果.该反应体系简单、催化效率高,不需要其它共催化剂.
三叔丁基膦亚胺苯氧钛配合物及其乙烯聚合性能
王铁石, 陈建军, 叶霖, 张爱英, 冯增国
2018, 38(6): 1544-1548  doi: 10.6023/cjoc201801004
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摘要:
四种不同基团取代的苯酚锂盐分别与三叔丁基膦亚胺三氯化钛进行反应,制得相应三叔丁基膦亚胺苯氧钛配合物(t-Bu3)PNTi(OAr)Cl2[OAr=O-C6H54a),O-2,6-Me2C6H34b),O-2,6-i-Pr2C6H34c)和O-2,6-t-Bu2C6H34d)],产物均借助1H NMR,13C NMR,31P NMR及元素分析进行了结构表征,并利用X射线单晶衍射确定了配合物三叔丁基膦亚胺三氯化钛(3),4b4d的分子结构.在助催化剂甲基铝氧烷(MAO)作用下,4a~4d对乙烯聚合均表现出高催化活性,并随配合物空间位阻增加而升高.4c热稳定性好,通过控制聚合反应条件,由此可以得到不同分子量及分子量分布的聚乙烯产物.
无碱条件下的Cu2O催化绿色氧化端基炔偶联
马楠, 曾祥华
2018, 38(6): 1556-1561  doi: 10.6023/cjoc201712038
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摘要:
无碱条件下,二甲基亚砜(DMSO)为溶剂,利用氧化亚铜在空气气氛中催化端基炔偶联,高效合成1,3-丁二炔类化合物,并研究了其反应机理.另外,该体系可放大至克级规模反应,且催化剂氧化亚铜可以回收利用.
姜黄中两个新没药烷型倍半萜成分的研究
黄超, 唐宇, 黄婷, 王立军, 江维, 麻光磊, 熊娟, 胡金锋
2018, 38(6): 1562-1565  doi: 10.6023/cjoc201712006
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摘要:
从购自安徽亳州中药材市场的姜黄(Curcuma longa L.)切片95%乙醇提取物中,除主要没药烷型倍半萜类成分芳姜黄酮[(+)-(S)-ar-turmerone]外,还分离得到2个新的同类化合物,turmerones E(1)和F(2).它们的结构通过质谱、一维/二维核磁共振谱和圆二色谱(ECD)等波谱和光谱技术得以确定.
NOTES
Synthesis and Anti-tumor Activities against HepG2 Cell in vitro of the Conjugates of Honokiol, Quercetin and Berberine
Shili Liao, Guogai Zhang, Han Cao, Biying Chen, Weimin Li, Xia Wu, Yifan Feng
2018, 38(6): 1549-1555  doi: 10.6023/cjoc201801023
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摘要:
Berberine, honokiol, quercetin are the lead compounds with outstanding anti-tumor activities. Three novel products were synthesized from honokiol, quercetin and berberine. The structures of the products were firstly confirmed by 1H NMR, 13C NMR, 2D NMR, HRMS, IR and UV. All products were evaluated for their anti-tumor activities against HepG2 cell in vitro and the results showed that the inhibitory effects of two compounds on HepG2 cell were far superior to honokiol and berberine hydrochloride, and the anti-tumor activities were similar to the reference drug cisplatin. It means that compounds 1 and 2 are expected to be the potential anti-tumor drugs.
亮点介绍
亮点介绍(6)篇
2018, 38(6): 1566-1568
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摘要: