铜催化羧酸与芳氨基甲酰氯的脱羧交叉偶联（英文）

报道了在不加碱的条件下,无配体铜盐能有效催化羧酸和氨基甲酰氯脱羧交叉偶联反应,以CuCl_2为催化剂、苯为溶剂,于120℃条件下反应48h即可实现脱羧交叉偶联过程.在此标准条件下,该催化体系对官能团普适性较好,以较高收率获得了各种酰胺,产物经~1H NMR、~(13)CNMR和HRMS表征     

铜催化α,β-不饱和羧酸与ICH2 CF3的脱羧偶联反应

铜催化下,以CH₃CN和HOAc为混合溶剂,α,β-不饱和羧酸与1,1,1-三氟-2-碘乙烷（ICH₂CF₃）发生脱羧偶联反应合成了一系列三氟乙基取代烯烃,其结构经¹H NMR、¹³C NMR和HR-MS确证。¹⁹F NMR分析显示该反应具有优良的立体选择性（E/Z最高为99/1）,分离收率最高达82%。     

脂肪族羧酸脱羧偶联反应研究进展

脱羧偶联反应是构建碳-碳键、碳-杂键以及活化碳-氢键的有效方法。该反应类型使用羧酸或羧酸盐作为底物,在催化剂的作用下可脱去二氧化碳并与其它化合物进行偶联反应。与传统的偶联反应相比,脱羧偶联反应具有对环境污染小、底物来源广等优点,因此该类型反应引起了研究者们的广泛关注。以芳香族羧酸进行的脱羧偶联反应已被报道,本文综述了近十年来各类催化体系下脂肪族羧酸进行脱羧偶联反应的研究进展。     

烟酰胺碳核苷类似物的模块化合成

以核糖异头羧酸制备为起始,以可见光/金属镍双重催化脱羧偶联反应为核心,与氰基水解反应相结合,开发了一条新的模块化合成路线,实现了一系列苄基保护烟酰胺碳核苷类似物的高效合成,其结构经¹H NMR, ¹³C NMR和HR-MS( ESI)表征。      

蒙脱土负载Pd/Cu双金属纳米微粒催化Sonogashira偶联反应

为了证实过渡金属催化碳碳键交叉偶联反应的双金属效应,首次研究蒙脱土负载纳米钯铜双金属微粒催化Sonogahira交叉偶联反应.结合蒙脱土重金属吸附特性与DMF溶剂热羰化还原,发展了一种新的双金属纳米微粒合成方法,制备了钯铜比例为1∶1的双金属纳米微粒.催化条件优化实验发现,乙二醇二甲醚/水(V∶V=1∶4)混合体系为最佳溶剂.碳酸钾与三苯基膦存在下,MMT@Pd/Cu高效催化芳基碘与系列端炔的交叉偶联反应,以较好产率分离得到15个炔烃衍生物.动力学研究表明,水对蒙脱土片层的溶胀作用与Pd/Cu双金属协同效应是该催化剂高活性的关键.     

饱和开链醚的氧化碳氢炔基化研究

首次报道了饱和开链醚和末端炔的交叉脱氢偶联.在Ph₃CCl/GaCl₃介导的温和氧化条件下,饱和开链醚与一系列芳基和烷基末端炔在室温可发生交叉脱氢偶联,反应收率高达73%.鉴于烷基乙炔反应效率较低的问题,还报道了Ph₃CCl/GaCl₃介导的饱和开链醚和一系列烷基取代的炔基硼试剂的氧化偶联,并获得了较好的反应收率.     

氮、硫双齿配体钯促进的Suzuki-Miyaura交叉偶联反应

钯配合物促进的Suzuki-Miyaura交叉偶联反应为构建碳-碳骨架的重要方法,主要用于药物化学、天然产物、材料学及超分子配体等领域。以2-噻吩甲醛、脂肪族/芳香族伯胺、取代肼及羟胺等为原料,合成了9种2-噻吩甲醛亚胺类N,S-双齿配体（3a~3i）,其结构经¹H NMR, ¹³C NMR和HR-MS（APCI）表征。并以N-环己基-2-噻吩甲亚胺(3b)为例,研究了配体对钯促进的Suzuki-Miyaura交叉偶联反应的催化性能。结果表明：在反应体系Pd(OAc)₂/3b/Cs₂CO₃/DMF中,苯硼酸与芳溴的交叉偶联反应的分离产率达到95%。     

银催化的脱羧性偶联反应研究进展

过渡金属催化的脱羧性偶联反应已成为有机合成中一种非常重要的合成策略.结合本课题组的工作,探讨了银催化脱羧反应在Hunsdiecker型卤代反应、碳-碳键构筑、碳-杂键构筑、C—H键官能团化等方面的新应用,综述了近几年脂肪羧酸、α-酮酸和芳香羧酸的银催化脱羧性偶联反应领域的研究新进展.银催化剂可以在过硫酸盐或其他氧化剂协同作用的辅助下,引发自由基历程的选择性脱羧偶联,反应具有操作简单、无需隔绝水和空气、反应条件温和等特点,是一种可调控的自由基反应.     

可见光光催化:缺电子杂环、苯环与芳基偶氮盐的直接芳基化偶联反应

发展了可见光照射下Ru(bpy)₃(PF₆)₂催化缺电子杂环C-H活化与芳基偶氮盐的交叉偶联反应.在室温、可见光照射下,各种缺电子杂环与芳基偶氮盐发生高效的偶联反应,同时在相似的条件下,普通苯环也能有效地与芳基偶氮盐偶联形成新C-C键化合物.     

镍催化构筑C(sp3)—C(sp3)键反应研究进展

过渡金属催化的偶联反应是构筑C-C键的高效方法,在有机合成中得到了广泛的应用.然而,相对于Heck反应、Negishi偶联与Suzuki偶联等构筑C（sp²）-C（sp²）键的反应,过渡金属催化的构筑C（sp³）-C（sp³）键的偶联反应较难进行,发展较晚.近年来,烷基-烷基C-C键偶联反应受到广泛的重视,一些高效催化剂被开发出来,其中镍催化剂展示出独特的催化活性和选择性.本文将综述镍催化烷基-烷基C-C键偶联反应最新研究进展,主要包括烷基亲电试剂与金属有机试剂交叉偶联反应、导向基参与的C（sp³）-H键活化的偶联反应、镍-光反应催化剂协同催化偶联反应、烷基亲电试剂与亲电试剂的还原偶联反应和镍催化烯烃加成反应等.     

Facile synthesis of a 4-anilinoquinazoline dimer by Suzuki cross-coupling reaction

A novel 4-anilinoquinazoline dimer linked by a carbon-carbon bond in the C-7 position was synthesized via a one step Suzuki cross-coupling reaction. All structures of new compounds were characterized by ¹H NMR, ¹³C NMR, and HRMS. The inhibition rate of the synthetic 4-anilinoquinazoline dimer 8 against epidermal growth factor receptor-tyrosine kinase enzymes (EGFR) in vitro was 44.4% at the concentration of 5.5 μmol/L.     

Facile synthesis and characterization of a novel thiophene-fused polycyclic aromatics based on pyrene

A novel large thiophene-fused polycyclic aromatics 1 based on pyrene 5 has been synthesized,and its structure was confirmed by ¹H NMR,¹³C NMR,MS,UV -vis and elemental analysis.The key steps of the synthesis involved the Stille cross-coupling reaction and followed by selectiveβ-βoxidative cyclization of pendant thienyl rings by FeCl₃ under mild conditions.     

烟酰胺腺嘌呤二核苷酸(NAD~+)类似物的合成及性质

合成了3种新型结构稳定的烟酰胺腺嘌呤二核苷酸(NAD~+)类似物并通过~1H NMR、~(13)C NMR、~(31)P NMR和HRMS进行了表征。NAD~+类似物经80℃加热24 h后,通过~1H NMR确认其结构稳定;通过循环伏安法(CV)测定了其电化学性质,表明其仍然具有良好的氧化还原性能。     

A novel entry into a new class of spiroheterocyclic framework: regioselective synthesis of dispiro[oxindole-cyclohexanone]pyrrolidines and dispiro[oxindole-hexahydroindazole]pyrrolidines

2,6-Bis(arylmethylidene)cyclohexanones undergo a regioselective 1,3-dipolar cycloaddition reaction with the azomethine ylide derived from isatin and sarcosine by a decarboxylative route affording a series of 1-N-methyl-spiro[2.3¹]oxindole-spiro[3.2¹¹]6¹¹-arylmethylidenecyclohexanone-4-aryl-pyrrolidines which were further annulated to give a series of novel 1-N-methyl-spiro[2.3¹]oxindole-spiro[3.7¹¹](3¹¹-aryl)Δ^111,711a-hexahydro-2H-indazole-4-aryl-pyrrolidines. The structures of which were established by spectroscopic techniques as well as single crystal X-ray analysis.     

A new C27-steroidal glycoside from Ophiopogon japonicus

A new C27-steroidal glycoside with three known compounds were isolated from the tuber of Ophiopogonjaponicus （Thunb.） Ker-Gawl. Based on the spectral analysis, including HRMS, 1H NMR, 13C NMR, DEPT, 1H-1H COSY, HMQC and HMBC, their chemical structures were determined as pennogenin-3-O-α-L-rhamnopyranosyl-（1→ 2）-β-D-xylopyranosyl-（1→ 4）-13-D-gluco- pyranoside （1）, pennogenin-3-O-α-L-rhamnopyranosyl-（1→ 2）-β-D-glucopyranoside （2）, ophiopojaponin C （3） and ophiopogonin D （4）. 2007 Jian Zhong Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

Synthesis of new chiral 1,2,3,4-tetrahydroisoquinoline β-amino alcohols from L-DOPA

Four new chiral 1,2,3,4-tetrahydroisoquinoline-derived β-amino alcohols were synthesized from L-DOPA in good yields. The structures of the target compounds were confirmed by ^1H NMR, ^13C NMR and MS.     

PhI(OAc)2/I2-Mediated Decarboxylative C4-Amination of Coumarin-3-Carboxylic Acids via Csp2−H Dehydrogenative C−N Cross-Coupling under Ambient Conditions

An efficient and straightforward protocol for accessing a new series of functionalized 4-aminocoumarins from PIDA/I₂-mediated decarboxylative C₄-amination of coumarin-3-carboxylic acids via direct C_sp2−H dehydrogenative C−N cross-coupling with secondary amines under ambient conditions has been accomplished. The notable advantages of this protocol are the tolerance of diverse functional groups, mild reaction conditions at ambient temperature, moderate to good yields, short reaction times (in minutes), high regioselectivity, gram-scale applicability, and eco-friendliness. This is the first report of decarboxylative C_sp2−H cross-dehydrogenative C−N coupling of coumarin-3-carboxylic acids for synthesizing 4-aminocoumarins.     

The N and C solid state NMR study of intramolecular hydrogen bond in some Schiff bases

In present work set of eight Schiff bases derived from substituted salicylaldehydes and aliphatic and aromatic amines has been studied in the solid state by ¹⁵N and ¹³C CPMAS NMR methods. ¹⁵N CPMAS NMR measurement is especially useful for investigation of the tautomerism in the compounds considered, owing to the large difference in the nitrogen chemical shifts of OH and NH tautomers. In the solid state, four of the compounds examined were shown by ¹⁵N CPMAS NMR to exist as OH tautomeric forms, and the remaining four as the corresponding NH forms with different stage of proton transfer process, from oxygen to nitrogen site.

This was confirmed by ¹³C CPMAS. The results reported were compared with those obtained for only two compounds in CDCl₃ solutions (solubility problems).     

Synthesis and Electrochemical Behavior of Electroactive Bistetrathiafulvalene-attached Thiacalix[4]arene Assemblies

Tetrabromoalkylthiacalix[4]arenes(1a and 1b) reacted with excess bis(tetraethylammonium)-bis(1,3- dithiole-2-thione-4,5-dithiol)zincate(2) to give thiacalix[4]arene-thiones(3a and 3b) in the presence of Na₂S. Two novel bistetrathiafulvalene-attached thiacalix[4]arene assemblies(5a and 5b) formed via triethyl phosphite-mediated cross-coupling of thiacalix[4]arene-thiones(3a and 3b) and 4,5-biscyanoethylthio-1,3-dithiole-2-one(4). All the four new compounds were characterized by ¹H NMR, ¹³C NMR, IR, MS spectra and elemental analysis. Meanwhile, the structures of thiacalix[4]arene-thiones(3a and 3b) were identified by X-ray analysis. In addition, the cyclic voltammograms of the resulting thiacalix[4]arenes containing electroactive TTF units(5a and 5b) were provided.     

混合三烃基锡衍生物的研究(Ⅱ)─一丁基二环己基锡羧酸酯的合成、结构表征及生物活性

合成了21个混合三烃基锡羧酸酯。利用红外光谱、核磁共振谱(¹H,¹³C,¹¹⁹Sn)和质谱表征了化合物的结构。对取代苯甲酸酯化合物,锡原子的化学位移δ(¹¹⁹Sn)与苯环上取代基的Hammett常数有很好的线性关系。化合物的生物活性测定结果表明,它们具有高效杀螨活性。