合成他达那非的方法改进

以D-色氨酸甲酯盐酸盐为原料,经过Pictet-Spengler缩合、N-酰化以及环合反应,合成了磷酸二酯酶-5抑制剂--他达那非,总收率64%.在缩合反应中利用cis-和trans-产物在醇溶剂中的溶解性的差异完成分离,避免了非对映异构体的拆分.     

"一锅法"合成N-乙基咔唑乙酰化衍生物

以N-乙基咔唑为原料,通过“一锅法”合成了未见文献报道的单乙酰化衍生物3-乙酰基-9-乙基咔唑和双乙酰化衍生物3,6-二乙酰基-9-乙基咔唑,其结构经1H NMR,IR,MS和元素分析表征。     

"一锅法"合成叔胺

以氨基酸甲酯的盐酸盐为原料,用“一锅法”高产率地合成了一系列N-取代叔胺,其结构经1H NMR和MS表征。     

"一锅法"合成戊二烯甲酯

以丙烯醛和丙二酸为原料,经缩合反应制得戊二烯酸,产率52．2％。采用“一锅法”合成了戊二烯酸甲酯,产率52．8％。其结构经^1H NMR和IR确证。     

偶联试剂SMCC的一锅法合成

SMCC是一类含有N-羟基琥珀酰亚胺(NHS)活性酯和马来酰亚胺的双功能偶联剂,可以分别将含有巯基和氨基的化合物键接在一起,在生物及化学领域应用广泛。本文采用一锅法将反式氨甲环酸、马来酸酐在DMF作溶剂的条件下反应生成反式氨甲环酸的马来酰胺,再与三氟乙酸酐、N-羟基丁二酰亚胺、三甲基吡啶等反应生成SMCC,对合成SMCC的工艺进行了简单优化,得出了最佳合成条件,总收率可达92%,纯度可达99%以上。     

一锅法简便合成取代苯氧基苯乙酮

探讨了聚合物支载的铬（Ⅵ）氧化剂、过溴离子及取代苯氧基离子于单锅中以1－苯乙醇为底物,合成苯氧基苯乙酮的方法,并与分步合成法相比较。实验表明,此合成方法具有操作简便、反应条件温和、无须分离中间体、且产率较高等优点,并探索了温度、溶剂、树脂的用量等对一锅法产率的影响。     

"一锅法"合成5-氟-2-羟基-苯乙酮

对合成5-氟-2-羟基-苯乙酮的方法进行改进,将原来的两步反应合并为一步,去掉了中间产物酯的繁琐分离和纯化,大大缩短了反应时间,操作简便,收率88．9％,适用于工业化生产。     

超声波促进的"一锅法"合成烯糖

在超声波促进下,未保护的吡喃糖依次与乙酸酐(或苯甲酸酐),乙酰溴,锌粉和PEG-600反应,"一锅法"合成了一系列乙酰化烯糖(或苯甲酰化烯糖).收率46%～89%,其结构经1H NMR确认.     

阿魏酸甲酯的一锅法绿色合成

以香兰素、丙二酸二乙酯为主要原料,以甘氨酸为催化剂,无水甲醇为溶剂,经水解、酸化和Knoevenagel缩合等反应一锅式合成了阿魏酸甲酯。较适宜的反应条件为n(香兰素):n(丙二酸二乙酯):n(甘氨酸)=1.0:1:8:0.15、反应时间8 h、甲醇用量110ml,产率72.3%。     

“一锅煮”选择性合成3′-O-(4-甲氧苯甲酰基)蔗糖及其类似物

二氯化钴催化经氢化钠活化的蔗糖与芳基酸酐反应,选择性地在蔗糖3′-OH上引入芳香酰基,通过"一锅煮"合成了3′-O-(4-甲氧苯甲酰基)蔗糖(3a,中药远志的抗抑郁活性成分)及其类似物3′-O-(3-甲基苯甲酰基)蔗糖(3b)和3′-O-(4-氯苯甲酰基)蔗糖(3c),收率54%～59%,其结构经1H NMR,13C NMR和ESI-MS表征。3a为首次化学合成的与相应天然产物结构相同的化合物,3b和3c未见文献报导。     

Improved Synthesis of Capuramycin and Its Analogues

Capuramycin and its congeners are considered to be important lead molecules for the development of a new drug for multidrug‐resistant (MDR) Mycobacterium tuberculosis infections. Extensive structure–activity relationship studies of capuramycin to improve the efficacy have been limited because of difficulties in selectively chemically modifying the desired position(s) of the natural product with biologically interesting functional groups. We have developed efficient syntheses of capuramycin and its analogues by using new protecting groups, derived from the chiral (chloro‐4‐methoxyphenyl)(chlorophenyl)methanols, for the uridine ureido nitrogen and primary alcohol. The chiral nonracemic (2,6‐dichloro‐4‐methoxyphenyl)(2,4‐dichlorophenyl)methanol derivative is a useful reagent to resolve rac‐3‐amino‐1,3‐dihydro‐5‐phenyl‐2H‐1,4‐benzodiazepin‐2‐one, the (S)‐configuration isomer of which plays a significant role in improving the mycobactericidal activity of capuramycin.     

蝴蝶霉素及其类似物的化学合成进展

蝴蝶霉素是一种新型的天然抗生素,由于具有特殊的抗肿瘤活性而引起了人们的关注。然而,由于一些不利因素导致蝴蝶霉素无法直接运用于临床。为了寻找活性更好的药物先导化合物,人们对蝴蝶霉素的结构进行修饰和改造,通过生物方法和化学方法,合成了大量的类似物。本文将从化学合成角度出发,立足蝴蝶霉素及其类似物结构构造的关键步骤,对近年来的合成研究进行综述。     

香豆素类抗凝血药及其类似物的合成

香豆素类抗凝血药及其类似物的合成;羟基香豆素;取代苯丁烯酮;缩合;香豆素类似物     

蚜虫警戒素及其类似物的合成

啬薇长管蚜、豌豆蚜、麦二叉蚜、棉蚜和桃蚜、谷长管蚜等蚜虫的警戒素都是倍半萜类化合物（Ｅ）７,１１二甲基３亚甲基１,６,１０十二碳三烯（Ｅ）βＦａｒｎｅｓｅｎｅ［１,２］．通过合成［３～５］并施放蚜虫警戒素以扰乱蚜虫的信息传递,并集中捕...     

Synthesis and Biological Evaluation of Lactimidomycin and Its Analogues

The studies culminating in the total synthesis of the glutarimide‐containing eukaryote translation elongation inhibitor lactimidomycin are described. The optimized synthetic route features a Zn^II‐mediated intramolecular Horner–Wadsworth–Emmons (HWE) reaction resulting in a highly stereoselective formation of the strained 12‐membered macrolactone of lactimidomycin on a 423 mg scale. The presence of the E,Z‐diene functionality was found to be key for effective macrocyclizations as a complete removal of these unsaturation units resulted in exclusive formation of the dimer rather than monocyclic enoate. The synthetic route features a late‐stage installation of the glutarimide functionality via an asymmetric catalytic Mukaiyama aldol reaction, which allows for a quick generation of lactimidomycin homolog 55 containing two additional carbons in the glutarimide side chain. Similar to lactimidomycin, this analog was found to possess cytotoxicity against MDA‐MB‐231 breast cancer cells (GI₅₀=1–3 μM) using in vitro 2D and 3D assays. Although lactimidomycin was found to be the most potent compound in terms of anticancer activity, 55 as well as truncated analogues 50 – 52 lacking the glutarimide side‐chain were found to be significantly less toxic against human mammary epithelial cells.     

Synthesis of Glycerophospholipid Conjugates of Cantharidin and Its Analogues

A series of glycerophospholipid conjugates of cantharidin and its analogues were synthesized in a one-pot reaction, using hexaehtyl phosphorus triamide, activated by a catalytic amount of iodine, as the phosphorylating reagent. The structures of the title compounds were confirmed by H NMR, ³¹P NMR, IR and elemental analysis.     

Synthesis of (+/-)-Epibatidine and Its Analogues

A nonopiate analgesic, epibatidine (1), isolated from the skin of the Ecuadoran poison frog was synthesized in racemic form starting from tropinone. Distinctly different from the previously published approaches, this synthesis features the novel synthesis of the 7-azabicyclo[2.2.1]heptane ring system by contraction of the tropinone skeleton viaFavorskii rearrangement. Five analogues of 1 were also prepared, and their analgesic activities were evaluated.     

倍半萜EnglerinA及其类似物的合成

2008年从东非大戟科属植物Phyllanthus engleri 中分离的吉玛烷型倍半萜(-)-englerin A对6种肾脏癌细胞展示了非常好的抑制活性(GI₅₀:1-87nm),甚至比紫杉醇的抗癌活性高1-2个数量级。这类倍半萜因其结构特点和显著的抗癌活性引起了有机化学界的广泛关注, 短短几年之内,就有多条全合成路线先后被报道。本文主要综述了(-)-englerin A及其类似物的合成进展,按照各个研究小组运用的关键策略加以分类,来阐述他们各自的合成特点。     

抗HIV天然产物Calanolide A及其类似物的合成进展

Calanolide A是从藤黄科红厚壳属植物(Calophyllum lanigerum)中分离的一种吡喃型香豆素类化合物, 对HIV-1- RT有很强的抑制作用, 是目前抗HIV的热点先导物. 综述了该化合物及其类似物的全合成研究进展, 分析了它的合成路线, 讨论了各合成方法的优缺点.