M(OTf)_3催化N－烷氧羰基吡咯或噻吩醛和盐酸伯胺的新颖Mannich反应

三氟甲磺酸盐M(OTf)_3 (M = Sc, Y, Ln)在水相中能较好地催化N－烷氧羰基 吡咯或噻吩与甲醛和盐酸伯胺的新颖的Mannich反应，其中Y(OTf)_3催化效果最佳 。该反应具有条件温和，收率较高和原子经济性等优点，为N－烷氧羰基吡咯和噻 吩类Mannich碱的合成提供了一种新方法，同时该反应以水为主要溶剂溶剂，符合 当今绿色化学的发展趋势。     

M(OTf)_3催化N－烷氧羰基吡咯或噻吩醛和盐酸伯胺的新颖Mannich反应

三氟甲磺酸盐M(OTf)_3 (M = Sc, Y, Ln)在水相中能较好地催化N－烷氧羰基 吡咯或噻吩与甲醛和盐酸伯胺的新颖的Mannich反应,其中Y(OTf)_3催化效果最佳 。该反应具有条件温和,收率较高和原子经济性等优点,为N－烷氧羰基吡咯和噻 吩类Mannich碱的合成提供了一种新方法,同时该反应以水为主要溶剂溶剂,符合 当今绿色化学的发展趋势。     

Zn/Y双金属接力催化:一锅法分子内环异构化/分子间阿尔德-烯反应构建α-羟基酰胺噁唑衍生物

报道了一种新型的Zn/Y双金属接力催化的串联反应,该方法通过Zn(OTf)₂和Y(OTf)₃接力催化,一锅法进行分子内环异构化/分子间阿尔德-烯反应构建α-羟基酰胺噁唑衍生物.产物的形成主要是由Zn(OTf)₂活化炔丙基酰胺的叁键发生分子内的环化反应构建噁唑啉中间体,由Y(OTf)₃催化1-苄基吲哚啉-2,3-二酮类化合物,继而由噁唑啉中间体与1-苄基吲哚啉-2,3-二酮类化合物发生分子间阿尔德-烯反应,实现了α-羟基酰胺噁唑衍生物的合成.优化部分的对比实验证实,Zn(OTf)₂和Y(OTf)₃的存在对于该串联反应都是必须条件.所有反应都是将各反应物和试剂一次性加入,在空气氛围下100℃加热进行反应.该方法反应条件简单、原子经济性高、官能团兼容性好,对噁唑衍生物合成具有重要的意义.     

稀土化合物Yb(OTf)3催化的有机合成反应的最新进展

研究和开发环境友好的有机合成反应是"绿色化学"研究的一个重要内容,其中也包括新型绿色催化剂的研究.本文对近两年来Yb(OTf)3作为催化剂的有机合成反应按照反应类型进行了综述.进一步总结和拓展了Yb(OTf)3的催化范围,证明了稀土化合物广泛的应用前景.     

高效且环境友好的催化剂—CMC负载稀土催化剂在一锅法合成咪唑类衍生物中的应用

CMC负载稀土催化剂是由CMC和异丙氧基稀土制得。这种固体Lewis酸催化剂被用在比较温和的条件下合成取代的咪唑类化合物。相比于昂贵的稀土Lewis酸Ln(OTf)3，廉价的CMC负载稀土催化剂也显示出了很高的催化活性。此外，这种催化剂还具有易于回收和重复使用五次以上没有明显失活的优点。     

二茂基环己氧基稀土化合物的合成、分子结构和催化活性

通过Cp_3Ln(Ln=Sm, Yb)和环己醇在THF溶剂中按1：1摩匀比反应，合成了标题 化合物[Cp_2LnOC_6H_(11)]_2(Ln=Sm, Yb)。化合物经元素分析、红外光谱分析表 征。镱配合物经X单晶衍射分析。它是一个以氧原子为桥的二聚体，环己烷基呈椅 式构型，O－C（环己烷基）键处于平伏e键位置。在上述基础上，尝试了它对己内 酯的催化聚合反应，发现标题化合物对己内酯聚合具有一定的催化活性。进一步合 成了[Cp_2YbOC_6H_(11)]与己内酯的1：4预聚反应产物，发现预聚物催化己内酯聚 合活性比标题化合物大大增强，从而说明催化聚合过程中引发反应速率慢是影响标 题化合物表观催化活性的重要因素。     

Fe(OTf)3催化含有N,O-缩醛结构硼酸酯的合成研究

报道了一种Fe(OTf)₃催化含有N,O-缩醛结构硼酸酯的简便合成方法,反应过程历经路易斯酸催化亚胺鎓与有机硼酸室温进行加成反应,以58%～98%的收率生成了一系列N,O-缩醛硼酸酯化合物.实验结果表明产物具有硼酸酯的性质,可以进行偶联反应.     

手性磷酸控制的不对称碳氢芳基化反应合成平面手性二茂铁化合物

报道了钯催化的分子内不对称C—H键芳基化反应.以简单易得的二茂铁羰基化合物为底物,Pd(CH_3CN)_4(OTf)_2为催化剂,使用手性磷酸作为唯一手性源,Buchwald类型联苯单膦配体,甲苯作溶剂,100℃进行反应,得到一系列二茂铁化合物,ee值最高可达83%.该反应为合成平面手性二茂铁化合物提供了一种新途径.     

Recent Advances in Organic Reactions Catalyzed by Lanthanide（Ⅲ） Complexes

Lanthanide compounds have been attracting much attention in organic synthesis.Chiral Ln-substituted BINOL have been widely studied in several asymmetric organic reactions.LnCl3 and Ln(OTf)3 have been expected to serve as Lewis acide and have been applied to many important synthetic reactions in a one-pot manner,Ln(O-i-Pr)3 exhibits some basic characters,which also can be utilized in some special organic transformation.This article deals with some lanthanides(Ⅲ）complexes promoted organic reactios,which we have recently developed.     

Ln(η~6-C_6H_6)(AlCl_4)_3对苯烷基化反应的催化作用

研究了中性芳烃稀土配合物Ln(η6 C6 H6 ) (AlCl4) 3(Ln =La ,Nd)对苯烷基化反应的催化作用。Ln(η6 C6 H6 ) (AlCl4) 3 可在温和条件下催化苯与己烯反应给出正己基苯和仲己基苯。探讨了不同催化剂及反应条件对此反应的影响。     

稀土-异烟酰肼席夫碱配合物的设计、合成与结构

由异烟酰肼和2-吡啶甲醛合成了席夫碱配体HL,并和稀土离子合成组装得一系列稀土配合物。用X-射线单晶衍射对配合物的结构进行了测定。通过荧光测试发现La配合物有荧光,而Eu,Dy则使配体的荧光淬灭。     

含氨基酸单元的手性主体的合成及手性识别研究

以L-丙氨酸和2,7-二萘酚为原料通过简单的方法合成了二种带有荧光基团萘的手性阴离子主体(1和2), 用红外光谱、质谱、元素分析、核磁共振氢谱及碳谱表征了它们的结构. 用荧光光谱及核磁共振氢谱研究了主体与二苯甲酰酒石酸阴离子的相互作用, 结果表明1, 2与D-或L-二苯甲酰酒石酸阴离子均形成1∶1的配合物, 主体1展现出良好的对二苯甲酰酒石酸阴离子对映选择性识别能力.     

手性胺醇稀土配合物的合成、荧光性质及其催化芳香酮的不对称氢化反应

合成了三种新的含C₂-对称轴的手性胺醇(PhOHCHCH₂)₂NCH₂C₆H₄R (R＝OCH₃, L₁; R＝CH₃, L₂; R＝Cl, L₃), 将其与无水氯化稀土LnCl₃•4THF (Ln＝La, Sm, Gd)反应生成了九个新的胺醇类稀土配合物LLnCl•2THF (L＝L₁, L₂, L₃; Ln＝La, Sm, Gd). 用元素分析、热重分析、红外和紫外光谱等手段对它们进行了表征. 荧光光谱显示一些配合物具有荧光性能. 原位催化芳香酮的不对称氢化反应表明: L₁/SmCl₃•4THF体系催化苯乙酮不对称氢化反应的转化率达71%, 相应的对映体过量值达32%.     

Synthesis,Characterization, Antimicrobial Activities,and Structural Studies of Lanthanide (III) Complexes with 1-(4-Chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone

Twelve coordinate lanthanide (III) complexes with the general composition [Ln L₃X_n(H₂O)_n] where Ln = Pr(III), Sm(III), Eu (III), Gd (III), Tb (III), Dy (III), X = Cl^?1, NO₃ ^?2, n = 2–7, and L is 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1- thiosemicarbazone have been prepared. The lanthanide complexes (5) were derived from the reaction between 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone (4) with an aqueous solution of lanthanide salt. Chalcone thiosemicarbazone ligand (4) was prepared by the reaction of [1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)]prop-2-enone (chalcone) (3) with thiosemicarbazide in the presence of hot ethanol. All the lanthanide-ligand 1:3 complexes have been isolated in the solid state, are stable in air, and characterized on the basis of their elemental and spectral data.

Thiosemicarbazone ligands behave as bidentate ligands by coordinating through the sulfur of the isocyanide group and nitrogen of the cyanide residue. The probable structure for all the lanthanide complexes is also proposed. The chalcone thiosemicarbazone ligands and their lanthanide complexes have been screened for their antifungal and antibacterial studies. Some of the synthesized lanthanide complexes have shown enhanced activity compared with that of the free ligand.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis,characterization and fluorescence of lanthanide Schiff-base complexes

Six new lanthanide Schiff-base complexes were synthesized by reactions of hydrated lanthanide nitrates with H₂L (H₂L?=?N,N′-bis(salicylidene)-1,2-cyclohexanediamine) and characterized by elemental analysis, DTA–TG, IR, UV and luminescence spectra. The microanalyses and spectroscopic analyses indicate a 1D polymeric structure with the formula of [Ln(H₂L)(NO₃)₃(MeOH)₂] _n [Ln?=?La (1), Ce (2), Pr (3), Sm (4), Gd (5) & Dy (6)]. The fluorescence spectrum of complex 4 exhibited Sm³⁺ centered, Schiff-base sensitized orange fluorescence, indicating that energy levels of the triplet state of H₂L match closely to the lowest excited state (⁴G_5/2) of Sm³⁺ ion.     

Synthesis and spectroscopic investigation of some dimeric coumarin and furanocoumarin models

Summary The synthesis of some dimeric coumarin and furanocoumarin models and their structure elucidation by¹H NMR,¹³C NMR, and mass spectroscopy is presented. In the presence of moisture some aldehydes are accompanied by their hydrates. Methoxy signal doubling in the presence of a chiral lanthanide shift reagent proves the dimeric nature of compound8. In the mass spectra, heterolytic cleavage of the O-C linkage was noticed which is a rare fragmentation in the case of aromatic ethers.

---

Synthese und spektroskopische Untersuchung einiger dimerer Cumarin- und Furanocumarinmodelle

Zusammenfassung Die Synthese einiger dimerer Cumarin- und Furanocumarin-Modellverbindungen und ihre Strukturaufklärung mit¹H- und¹³C-NMR- sowie Massenspektrometrie werden beschrieben. In Gegenwart von Feuchtigkeit werden einige der Aldehyde von ihren Hydraten begleitet. Verdoppelungen der Methoxy-¹H-Signale von8 in Anwesenheit eines chiralen Lanthanoid-Verschiebungsreagenzes beweisen, daß8 ein Dimer ist. In den Massenspektren finden sich Hinweise für heterolytische Spaltungen der O-C-Bindungen. Solche Fragmentierungen sind bei aromatischen Ethern ungewöhnlich.

     

Synthesis of Unsymmetrical Schiff-Base Porphyrin with O-Nitrobenzaldehyde and its Lanthanide Complexes

The synthesis of a new unsymmetrical Schiff-base porphyrin is reported from 5-(p-nitrophenyl)-10, 15, 20-triphenyl porphyrin and o-nitro benzaldehyde. Its lanthanide complexes are also reported. The ligand and its lanthanide complexes are characterized by UV, IR and ¹H NMR spectra.     

模板分子诱导的微孔镧系-2-羧基肉桂酸超分子配合物的合成与结构

由水热法合成了2个微孔镧系超分子配合物[Ln(CCA)(OH)(phen)(H2O)]n·n(phen)·nH2O(Ln=Yb,1;Er,2;H2CCA=2-羧基肉桂酸;phen=1,10-菲啰啉),并用元素分析、IR及X-射线单晶衍射对其进行了表征。晶体结构研究表明,2个配合物都是由配体2-羧基肉桂酸连接而形成的一维双链结构,该链状结构通过氢键和π-π堆积作用扩展为具有微孔结构的超分子。1,10-菲啰啉在微孔结构的形成过程中起到了模板剂的作用。     

Stereochemistry and solid-state circular dichroism spectroscopy of eight-coordinate chiral lanthanide complexes

Eight-coordinate chiral lanthanide complexes [Eu(dbm)₃L ^RR ] (1), [Eu(dbm)₃L ^SS ] (2) and [Tb(dbm)₃L ^RR ] (3) (L ^RR /L ^SS = (-)-/(+)-4,5-pineno-2,2′-bipyridine, Hdbm = dibenzoylmethane) were synthesized stereoselectively, which were characterized by UV-vis, CD spectra and X-ray single-crystal diffraction. The mirror-image structure features of complexes 1 and 2 were obtained by combination of the solid-state CD spectra and the crystal structure analysis. After further comparison with the solid-state CD spectra of six-coordinate and seven-coordinate metal complexes containing β-diketone ligands, the CD spectra-absolute configuration correlation rule for the eight-coordinate β-diketonate lanthanide complexes was proposed through the exciton chirality method for the first time. The Δ or Λ absolute configurations of complexes 1–3 with the distorted square antiprism geometry were confirmed by the X-ray single-crystal analysis.     

Synthesis,crystal structures and thermal decomposition kinetics of four new lanthanide complexes with 3,4-dimethylbenzoic acid and 1,10-phenanthroline

A new series of lanthanide complexes [Ln(3,4-DMBA)₃phen]₂ [Ln(III) = Nd(1), Sm(2), Tb(3) and Dy(4), 3,4-DMBA = 3,4-dimethylbenzoate, phen = 1,10-phenanthroline] have been synthesized and characterized by elemental analysis, infrared spectra and TG-DTG techniques. The single crystals of the complexes 3 and 4 have been obtained and their structures have been determined by single-crystal X-ray diffraction. In the complexes 3 and 4, each Ln(III) ion is coordinated by four bidentate-bridging 3,4-DMBA ligands, one bidentate-chelating 3,4-DMBA group and one bidentate-chelating phen ligand, giving a coordination number of eight. The complex 3 shows bright green luminescence under ultraviolet light in the solid state. Thermal analysis of the complexes 1–4 are discussed by TG-DTG and IR techniques. The non-isothermal kinetics of the complexes 1–4 are investigated by using double equal-double step method. The thermodynamic parameters (ΔH ^≠ , ΔG ^≠ and ΔS ^≠ ) and kinetic parameters (activation energy E and the pre-exponential factor A) of the four complexes are also calculated.