钯催化的有机卤化物的1,2-加成反应研究进展

钯催化有机卤代烃参与的对碳杂原子重键化合物的1,2-加成反应,可以有效避免传统Grignard反应、Barbier反应中活泼有机金属试剂的制备,简化合成操作并提高底物官能团的适应性,具有良好的应用前景。本文对近年来该类反应在合成化学中的发展进行了综述。     

KO~tBu促进的有机叠氮和末端炔烃的环加成反应改进研究

文章系统研究了叔丁醇钾促进下芳基叠氮和取代苯乙炔的环加成反应。在等摩尔数的叔丁醇钾作用下,当溶剂为DMF时,反应效果最佳,产率高达92%。其他的芳基叠氮和苯乙炔的反应研究结果表明,芳基叠氮和苯乙炔在此环加成反应中具有良好的反应适应性。     

相转移催化环加成反应合成1-芳磺酰基-2-苯甲酰基环丙烷系列化合物(Ⅰ)

苯甲酰硫叶立德对芳磺酰基乙烯的环加成合成了标题系列化合物，它们是一类生物活性物质。     

给体-受体环丙烷化合物的环加成反应研究

给体-受体环丙烷在有机合成中逐渐受到重视,目前大多数研究集中于分子之间的亲核取代反应。最常用的是在路易斯酸作用下,给体-受体环丙烷化合物开环,并与烯烃、炔烃、1,3-偶极子或其他不饱和化合物发生环加成反应。本文简单报道了传统的实现给体-受体环丙烷环加成反应的方法。     

金属有机骨架材料在催化中的研究进展

简介了金属有机骨架材料（MOFs）的合成方法,主要介绍了MOFs应用于Lewis酸、碱和手性催化中的研究进展,对MOFs材料在催化领域的应用进行了展望。     

相转移催化环加成反应合成1-芳磺酰基-2-苯甲酰基环丙烷系列化合物(Ⅱ)

合成了芳磺酰基环及芳酰基环上含有三氟乙氧基的标题化合物。含氟基团的引入能增强其生物活性。     

金属有机骨架材料及其催化应用研究进展

从MOFs材料的催化应用方向出发,简述了MOFs材料及其发展历程,并介绍了MOFs材料的分类,包括以羧酸为配体的MILs、IRMOFs及UIOs等化合物,以含氮杂环为配体的ZIFs等化合物及其他复合材料;讨论了在光催化、电催化及生物催化等方面的应用。分析表明,MOFs材料在分解水产氢、产氧和二氧化碳还原等领域具有优异的性能,但也存在如成本较高、稳定性有待提高等问题。未来可重点关注MOF基催化剂稳定性、导电性等性能的进一步优化,可以通过调控其形貌或与其他半导体材料结合以使材料具有更优异的性能;同时高成本、回收困难等其他因素一直是限制MOFs材料工业应用的主要问题,需要研究人员继续攻克解决。     

乙烯和环烯烃共聚用有机金属催化剂

配位催化共聚是制备环烯烃共聚物的主要方法,目前商品化的环烯烃共聚物主要由乙烯与降冰片烯或者四环十二碳烯共聚得到。共聚单体及其含量是决定环烯烃共聚物性能的关键因素,而决定共聚单体含量的最核心因素是催化剂。本文从催化剂结构的角度出发,综述了乙烯和降冰片烯/四环十二碳烯共聚用有机金属催化剂,从双茂有机金属催化剂、单茂有机金属催化剂、非茂有机金属催化剂、后过渡金属催化剂等部分进行论述,同时论述了催化剂结构及关键聚合工艺（如温度、压力、单体浓度等）对催化活性及共聚单体插入量的重要影响。此外,由于乙烯与四环十二碳烯共聚活性低,未来针对该共聚反应的研究会继续进行。合成更多新结构的配体、开发更高活性的催化剂、构建更经济有效的反应体系将会是新的研究重点。     

α,β-不饱和酮与金属有机试剂的不对称共轭加成反应的研究进展

综述了近来α,β 不饱和酮与金属有机试剂的不对称共轭加成反应的研究进展。详细介绍了α,β 不饱和酮与金属试剂反应的配体及影响反应的条件。     

铜粉催化氰化物与NaN_3的环加成反应研究

文章研究了普通铜粉催化体系催化氰化物与NaN_3的[2+3]环加成反应。研究结果表明,以铜粉作为催化剂,Et_3N作为助催化剂,DMF/MeOH(9∶1)为溶剂,将氰化物与NaN_3于常压、温度为55~60℃下反应12 h,合成5-取代四唑化合物,其收率可达85%左右。该方法具有催化剂廉价易得且用量少、反应条件温和、耗时少、产率高、后处理操作简单等优点。     

Strain-promoted azide-alkyne cycloaddition “click” as a conjugation tool for building topological polymers

Strain-promoted azide-alkyne cycloaddition “click” reaction (SPAAC) was successfully used as a tool in synthesis of star polymers by grafting onto approach. The application of SPAAC method in star polymer synthesis was investigated for coupling reaction of the dibenzocyclooctyne (DIBO) end group of polystyrene (PS) and poly(ethylene glycol) (PEG) with coupling agents bearing 2, 3, or 4 azido groups. Firstly, well-defined linear DIBO-terminated PS was obtained by atom transfer radical polymerization (ATRP) of styrene using a DIBO containing ATRP initiator and linear DIBO-terminated PEG was obtained by terminal functionalization of PEG monomethyl ether (PEG-OH). Then a series of star PS and PEG bearing two, three and four arms were prepared respectively by subjecting SPAAC coupling reaction between the linear polymer-DIBO and the azido tethered core molecules at 30 °C without catalyst. The obtained star PS showed a well-defined structure after fractional precipitation to remove slightly excess linear polymers, and all the star polymers were characterized via Fourier transform infrared spectroscopy (FTIR), ¹H nuclear magnetic resonance spectroscopy (¹H NMR), size exclusion chromatography (SEC) and matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS).     

稀土金属有机骨架材料Yb-BTC催化合成聚碳酸酯二醇

以Yb(NO3)3·5H2O和均苯三甲酸(H3BTC)为原料,采用溶剂热法构筑了一种稀土金属有机骨架材料Yb-BTC。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、N2吸附-脱附技术和傅里叶变换红外光谱(FTIR)对其结构进行了表征。结果显示,Yb-BTC是一种典型的微孔材料,比表面积为560 m2/g,孔径为1.84 nm,颗粒尺寸大小均一,粒径约为2μm。考察了Yb-BTC在碳酸二苯酯(DPC)与1,5-戊二醇(PDO)酯交换制备聚碳酸酯二醇(PCDL)反应中的催化性能,并与三乙胺、醋酸锌、钛酸四丁酯和乙酰丙酮氧钛4种催化剂进行了比较。结果表明,Yb-BTC的催化活性与钛系催化剂活性相当。当PDO与DPC的物质的量比为1.2,Yb-BTC用量为0.05%(以DPC质量为基准,下同),180～185℃下常压酯交换反应2 h,160℃下减压缩聚4 h,获得数均相对分子质量为2300,羟值为49.3 mg KOH/g的PCDL。     

Conversion of CO into CO2 by high active and stable PdNi nanoparticles supported on a metal-organic framework

The solubility of Pd(NO₃)₂ in water is moderate whereas it is completely soluble in diluted HNO₃ solution. Pd/MIL-101(Cr) and Pd/MIL-101-NH₂(Cr) were synthesized by aqueous solution of Pd(NO₃)₂ and Pd(NO₃)₂ solution in dilute HNO₃ and used for CO oxidation reaction. The catalysts synthesized with Pd(NO₃)₂ solution in dilute HNO₃ showed lower activity. The aqueous solution of Pd(NO₃)₂ was used for synthesis of mono-metal Ni, Pd and bimetallic PdNi nanoparticles with various molar ratios supported on MOF. Pd₇₀Ni₃₀/MIL-101(Cr) catalyst showed higher activity than monometallic counterparts and Pd+ Ni physical mixture due to the strong synergistic effect of PdNi nanoparticles, high distribution of PdNi nanoparticles, and lower dissociation and desorption barriers. Comparison of the catalysts synthesized by MIL-101(Cr) and MIL-101-NH₂(Cr) as the supports of metals showed that Pd/MIL-101-NH₂(Cr) outperforms Pd/MIL-101-(Cr) because of the higher electron density of Pd resulting from the electron donor ability of the NH₂ functional group. However, the same activities were observed for Pd₇₀Ni₃₀/MIL-101(Cr) and Pd₇₀Ni₃₀/MIL-101-NH₂(Cr), which is due to a less uniform distribution of Pd nanoparticles in Pd₇₀Ni₃₀/MIL-101-NH₂(Cr) originated from amorphization of MIL-101-NH₂(Cr) structure during the reduction process. In contrast, Pd₇₀Ni₃₀/MIL-101(Cr) revealed the stable structure and activity during reduction and CO oxidation for a long time.     

Multicomponent Synthesis of 1,2,3‐Triazoles in Water Catalyzed by Copper Nanoparticles on Activated Carbon

Copper nanoparticles on activated carbon have been found to effectively catalyze the multicomponent synthesis of 1,2,3‐triazoles from different azide precursors, such as organic halides, diazonium salts, anilines and epoxides in water. The first one‐pot transformation of an olefin into a triazole is also described. The catalyst is easy to prepare, very versatile and reusable at a low copper loading.     

Cu基CO2合成甲醇催化剂载体的研究进展

氧化物载体与Cu之间的相互作用、CO₂的活化位点、表面反应机理、表面反应路径直接影响CO₂催化加氢的产物分布。因此,探明不同金属–载体的相互作用和界面微观结构至关重要。本文综述了CO₂催化加氢合成甲醇Cu基催化剂载体的研究现状,重点综述了ZnO、ZrO₂、CeO₂、TiO₂这4种具有氧空位的载体,并简单总结了SiO₂、Al₂O₃、Zn-Zr、Ce-Zr、钙钛矿等其他氧化物载体。Cu与ZnO之间的强金属相互作用（SMSI）所形成的Cu/ZnO_x是主要的活性位点,对其微观结构与反应机理研究得较为充分;对Cu/ZrO₂的研究主要集中在ZrO₂晶相的影响,不同的研究者所获得的结论尚存在争议;对Cu/CeO₂的机理研究停留在反向CeO₂/Cu(111)模型表面,负载型催化剂上不同晶面的CeO₂与Cu的相互作用强度不同,并影响反应性能;Cu/TiO₂中TiO₂的影响因素较多,如晶型、晶面等,目前对其研究尚不全面。最后,本文分析并展望了CO₂加氢制甲醇催化剂载体的研究方向,未来将采用与实际催化剂一致的正向模型表面进行基础研究,并基于原位表征手段对反应过程中催化剂的结构变化进行探索,最终设计高效、低成本的多元复合物载体的Cu基催化剂。     

Copper-alginates: a biopolymer supported Cu(II) catalyst for 1,3-dipolar cycloaddition of alkynes with azides and oxidative coupling of 2-naphthols and phenols in water

Copper(II) ions immobilized onto a biopolymer (sodium alginate) is an effective heterogeneous catalyst for 1,3-dipolar cycloaddition of alkynes with azides and oxidative coupling of 2-naphthols and phenols in water to afford the 1,4-disubstituted 1,2,3-triazoles and biaryl compounds respectively in good yields. The catalyst was recovered quantitatively by simple filtration and reused for several times without significant loss of activity.     

乙烯齐聚制α-烯烃的非均相催化剂

综述了乙烯齐聚制α-烯烃的非均相催化剂及其催化机理。主要论述了非均相催化剂载体、金属离子及其价态、活性中心和反应中间物的形成、助催化等对乙烯齐聚反应性能的影响,并对催化剂的结构与性质、催化机理进行了系统的研究,指出研究和开发乙烯齐聚非均相催化剂对其下游工业具有重大的战略意义。