Synthesis of Diethyl Oxalate by a Coupling—Regeneration Reaction of Carbon Monoxide

This article describes a process for the synthesis of diethyl oxalate by a copling reaction of carbon monoxide,catalyzed by palladium in the presence of ethyl nitrite ,The kinetics and mechanism of the coupling and regeneration reaction are also discussed ,This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation.     

“烯—二炔”模型化合物前体—6—硫杂—13—氧杂双环［9.3.0 …

以顺－１,２,３,６－四氢邻苯二甲酸酐为原料,经还原、环化、臭氧化、Ｗｉｔｔｉｇ羰基烯化、酯化、二醇化和硫化等８步反应,合成了新型抗癌抗菌素“烯－二炔”的双环前体：６－硫杂－１３－氧杂双环［９．３．０］－３,８－十四二炔。该合成路线步骤少,收率高,反应条件温和。６个新化合物４－９的结构均经元素分析、核磁共振、红外光谱和质谱确证。     

Palladium－catalyzed Cascade Cyclization－Coupling Reaction of Benzyl Halides with N, N－Diallylbenzoylamide

A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excellent yields.     

Synthesis of 4—Aryl—3,4—dihydropyrimidinones Using Microwaveassisted Solventless Biginelli Reaction

Ｉｎｔｒｏｄｕｃｔｉｏｎ4 Ａｒｙｌ 3,4 ｄｉｈｙｄｒｏｐｙｒｉｍｉｄｉｎｏｎｅｓ (4)ａｓａｃｏｒｅｗｅｒｅｏｂｓｅｒｖｅｄｉｎｓｏｍｅｂｉｏｌｏｇｉｃａｌｌｙｉｍｐｏｒｔａｎｔｃｏｍｐｏｕｎｄｓ .1Ｍｏｒｅｒｅｃｅｎｔｌｙ ,ｄｉｈｙｄｒｏｐｙｒｉｍｉｄｉｎｏｎｅｓａｒｅｓｈｏｗｎｔｏｂｅａｕｓｅｆｕｌｔｏｏｌｆｏｒｓｔｕｄｙｉｎｇｄｙｎａｍｉｃｃｅｌｌｕｌａｒｐｒｏｃｅｓｓａｎｄｃａｎｂｅｃｏｎｓｉｄｅｒｅｄａｓａｎｅｗｌｅａｄｆｏｒｔｈｅｄｅｖｅｌｏｐｍｅｎｔｏｆａｎｔｉ ｃａｎｃｅｒｄｒｕｇ…     

Synthesis of Flurbiprofen via Suzuki Reaction Catalyzed by Palladium Charcoal in Water

Flurbiprofen 1, an excellent nonsteroidal antiinflammatory drug, was synthesized in 5 steps in 69% overall yield. The key step of constructing the biaryl fragment was successfully achieved via Pd/C-catalyzed Suzuki coupling reaction in water using sodium tetraphenylborate as phenylation reagent.     

新杂环化合物6,20—二硫杂—13,27—二氯杂三环[23,3,0,0^11,15]—3,8,17,22—四

近年来,科学家先后从细菌分泌物中分离出几种含有环状"烯-二炔”的Calicheamicinγ1I[1～4]Esperamicin A1[5～7],Dynemicin A1[8]Neocarzinostatin 发色团[9～11],Kedarcidin发色团[12～13]等新型抗癌抗菌素,我们已做过评述[14].它们的"1,5-二炔-3-烯”部分经生物还原生成1,4-脱氢苯双自由基,从癌细胞DNA糖磷酯骨架上夺取氢原子,引起癌细胞DNA氧化断裂,杀灭癌细胞,因而有广泛的应用前景. 标题化合物是"烯-二炔”前体,以3,4-二(4′-甲磺酰氧-2′-丁炔基)四氢呋喃(1)为原料,在硫化钠作用下关环,得到了新杂环化合物(2).通过元素分析,红外光谱,质谱进行了分析,又进一步进行了1H NMR和13C NMR谱测定,并对其谱线进行归属,确证了结构.     

Soluble Polymer—supported Synthesis of Indoles via Palladium—mediated Heteroannulation of Terminal Alkynes with o—Iodoanilines

A soluble polymer-supported synthesis of indoles via palladium-mediated heteroannulation of terminal alkynes with o-iodoanilines has been described. The protocol provides a useful tool for constructing combinatorial indole libraries.     

Application of Suzuki Cross‐Coupling Reaction Catalyzed by Ligandless Palladium Chloride in the Synthesis of Liquid Crystals

Palladium chloride–catalyzed Suzuki cross‐coupling reaction was applied to the preparation of highly pure multiring liquid crystals with a biphenyl unit. The optimal reaction condition is the combination of 0.5 mol% PdCl₂, pyridine, and K₃PO₄, which was able to catalyze the cross‐coupling of substituted aryl bromides with substituted trans‐cyclohexylphenylboronic acids to give pure products in 38–87% yields.     

Clean Synthesis in Water：Darzens Condensation Reaction of Aromatic Aldehydes with Phenacyl Chloride

The Darzens condensation reaction of aromatic aldehydes with phenacyl chloride proceeded very efficiently in a water suspension medium in the presence of triethylbenzylammonium chloride and only trans-2,3-epoxy-1,3-diaryl-1-propanones were formed which can be isolated simply by filtration.The structures of these compounds were confirmed by elemental analysis,IR and ^1H NMR spectra.Therir configurations are in agreement with that of the same compounds reported in the literature.Compared to the classical Darzens condensation,this new method has the advantages of good yields,high stereoselectivity,low running cost inexpensive and environmentally benign procedure.     

钯催化偶合卟吩-并合杂环顺烯二炔二联体的合成

具有新颖共轭顺-烯二炔结构的天然产物可精巧地引发顺-烯二炔的闭环反应而产生双自由基,从癌细胞DNA糖磷脂骨架上夺取氢原子,促成病变细胞氧化断裂而产生强烈的抗癌功效（比阿霉素抗癌活性大4000倍）。作为保证抗肿瘤疗效的另一重要因素是提高抗癌药物对病变组织的选择性,基于用于光动力疗法（PDT）的抗癌药物卟啉类化合物识别和选择性富集于肿瘤细胞的特殊功能,     

焦脱镁叶绿酸甲酯的Vilsmeier反应合成δ-meso-甲酰乙烯基卟吩和苯并异细菌卟吩

From methyl pyropheophorbide-a (MPPa, 1), the vinyl group of methyl pyropheophorbide-a was converted into alkylcarbonyl group by Grignard reaction and oxidization to give chlorins 2, 3 and 5. The Vilsmeier reaction of nickel 3-substituent-3-devinylpyropheophorbide-a (6), which was prepared by the metallation with nickel acetate, with 3-dimethylamino-acrolein/phosphoryl chloride (3-DMA/POCl3) was carried out to give δ-meso-formylvinylpyropheophorbide-a (7) in good yield. The benzoisobacterichlorin (8) was obtained by the treatment of 7b with concentrated sulfuric acid.     

红紫素-18的卤化反应及其二氢卟吩类衍生物的合成

从红紫素-18甲酯开始,通过对其3-位乙烯基和20-meso-位的亲电加成和亲电取代反应,区域选择性地给出相应的氯代或者溴代产物.红紫素-18甲酯与重氮甲烷的1,3偶极环加成反应生成C(3)-吡唑啉基取代的红紫素-18,继续与N-溴代丁二酰亚胺(NBS)和N-氯代丁二酰亚胺(NCS)进行亲电取代反应,生成相应的卤代吡唑啉基取代二氢卟吩.3-吡唑啉基红紫素-18热裂解后的卤代反应则给出3-环丙基-20-卤代二氢卟吩.选择脱镁叶绿酸-a甲酯为另一起始反应物,通过C(3)-乙烯基和E-环结构的一系列化学转换和20-meso-位的溴代反应,区域选择性地得到20-溴代红紫素-18衍生物.新报道的标题化合物均经UV,IR,1H NMR及元素分析证明其结构.     

二氢卟吩e~6-6-酰胺衍生物的合成

首次报道了以蚕沙叶绿素初提物为基础原料,经酸降解得到含焦脱镁叶绿酸a和脱镁叶绿酸a的混合物,不经分离直接与胺类反应使脱镁叶绿酸a的戊酮环(V)裂开,合成得11种二氢卟吩e~6-6-酰胺衍生物。提供了一种合成二氢卟吩酰胺的新方法。     

具有叶绿素-a碳架的苯乙烯基取代Z/E-二氢卟吩衍生物的合成

The Wittig reaction of methyl pyropheophorbide-d 2,obtained from methyl pyropheophorbide-a 1,with ben-zyltriphenylphosphonium bromide was performed to yield isomers 3a and 3b.The Vilsmeier reaction of nickelcomplex 4 or 7 with 3-dimethylaminoacrolein in the presence of phosphoryl chloride was carried out to form20-meso-2'-formylvinylpyropheophorbide-a 5 or 8,which was reacted with Wittig reagent to afford nickel complexisomers 6a and 6b or 9a and 9b,10a and 10b.     

具有叶绿素-a基本碳架的氯代二氢卟吩衍生物的合成

选择脱镁叶绿酸-a甲酯为起始原料, 经过化学结构修饰转换成其他叶绿素-a衍生物. 以过氧化氢/盐酸、N-氯代丁二酰亚胺(NCS)、氯化氢(或者浓盐酸)为氯化剂, 根据3-乙烯基和20-meso-位的不同化学反应活性, 通过亲电加成和亲电取代反应, 在二氢卟吩环上选择性地引进氯原子, 完成8种未见报道的具有叶绿素-a基本碳架的氯代二氢卟吩衍生物的合成. 所合成的新化合物均经UV, IR, 1H NMR及元素分析证明其结构.     

焦脱镁叶绿酸的Knoevenagel反应及其杂环取代衍生物的合成

以焦脱镁叶绿酸-d甲酯(MPPd)为起始原料, 通过其醛基与连有五元杂环的β-二酮、α-氰基酮和丙二腈的活性亚甲基进行Knoevenagel反应, 完成3-位五元杂环取代的焦脱镁叶绿酸-a甲酯衍生物. 所合成的新化合物均经UV, IR, ¹H NMR及元素分析证明其结构.     

卟啉类第二代光敏剂的发展

本文对目前用于光动力治疗的以卟啉为基础的第二代光敏剂进行了综述, 这些光敏剂中的大部分已进入临床或临床前试验, 光物理性质研究表明它们是很有前途的光动力药物. 本文同样介绍了连接生物分子和硼烷的卟啉衍生物, 作为光疗剂, 它们具有非常光明的前途.     

Chlorin e6-Biotin Conjugates for Tumor-Targeting Photodynamic Therapy

To improve the tumor-targeting efficacy of photodynamic therapy, biotin was conjugated with chlorin e6 to develop a new tumor-targeting photosensitizer, Ce6-biotin. The Ce6-biotin had good water solubility and low aggregation. The singlet-oxygen generation rate of Ce6-biotin was slightly increased compared to Ce6. Flow cytometry and confocal laser scanning microscopy results confirmed Ce6-biotin had higher binding affinity toward biotin-receptor-positive HeLa human cervical carcinoma cells than its precursor, Ce6. Due to the BR-targeting ability of Ce6-biotin, it exhibited stronger cytotoxicity to HeLa cells upon laser irradiation. The IC50 against HeLa cells of Ce6-biotin and Ce6 were 1.28 µM and 2.31 µM, respectively. Furthermore, both Ce6-biotin and Ce6 showed minimal dark toxicity. The selectively enhanced therapeutic efficacy and low dark toxicity suggest that Ce6-biotin is a promising PS for BR-positive-tumor-targeting photodynamic therapy.     

C(3)-乙烯基的化学修饰与含氧基团取代的叶绿素-a衍生物的合成

以焦脱镁叶绿酸-a甲酯为起始原料, 通过加成和氧化反应将其3-位上的乙烯基转化为羟乙基、溴乙基、二羟乙基、二溴乙基和溴羟乙基, 再经过二甲亚砜/乙酸酐或者高钌酸四丙基铵(TPAP)/N-甲基吗啉-N-氧化物所组成的混合氧化剂的氧化反应, 得到多种C(3)-多酮基取代的二氢卟吩衍生物. 其单羟基作为离去基团与不同的活泼亚甲基化合物经过重排过程, 得到相应的酮基取代的二氢卟吩衍生物. 所得新叶绿素衍生物的化学结构均经UV, IR, ¹H NMR及元素分析得以证实, 并对相应的反应提出可能的反应机理.