Phase‐Transfer‐Catalysed Synthesis of Pyrroloindolines and Pyridoindolines by a Hydrogen‐Bond‐Assisted Isocyanide Cyclization Cascade

A cascade reaction that generates pyrrolo‐ and pyridoindoline motifs from isocyanide precursors under phase‐transfer conditions is described. This transformation proceeds at room temperature in the presence of a quaternary ammonium catalyst and base to generate functionalized products containing an all‐carbon quaternary stereocentre. Quantum chemical calculations demonstrated that intramolecular general acid catalysis plays a key accelerating role through stabilization of developing charge in the transition state, and that the reaction is best described as a 5‐endo dig cyclization, rather than an anionic 6π electrocyclization. Investigations employing chiral phase‐transfer catalysts have given promising selectivities to date.     

Semiconductor and Metallic Core–Shell Nanostructures: Synthesis and Applications in Solar Cells and Catalysis

Nano‐heterostructures have attracted great attention due to their extraordinary properties beyond those of their single‐component counterparts. This review focuses on a specific type of hybrid structures: core–shell structures. In particular, we present and discuss the recent wet‐chemical synthesis approaches for semiconductor and metallic core–shell nanostructures, and their relevant properties and potential applications in photovoltaics and catalysis, respectively.     

Tandem CH Activation/Arylation Catalyzed by Low‐Valent Iron Complexes with Bisiminopyridine Ligands

Tandem C?H activation/arylation between unactivated arenes and aryl halides catalyzed by iron complexes that bear redox‐active non‐innocent bisiminopyridine ligands is reported. Similar reactions catalyzed by first‐row transition metals have been shown to involve substrate‐based aryl radicals, whereas our catalytic system likely involves ligand‐centered radicals. Preliminary mechanistic investigations based on spectroscopic and reactivity studies, in conjunction with DFT calculations, led us to propose that the reaction could proceed through an inner‐sphere C?H activation pathway, which is rarely observed in the case of iron complexes. This bielectronic noble‐metal‐like behavior could be sustained by the redox‐active non‐innocent bisiminopyridine ligands.     

Thermal Ethane Activation by Bare [V2O5]+ and [Nb2O5]+ Cluster Cations: on the Origin of Their Different Reactivities

The gas‐phase reactivity of [V₂O₅]⁺ and [Nb₂O₅]⁺ towards ethane has been investigated by means of mass spectrometry and density functional theory (DFT) calculations. The two metal oxides give rise to the formation of quite different reaction products; for example, the direct room‐temperature conversions C₂H₆→C₂H₅OH or C₂H₆→CH₃CHO are brought about solely by [V₂O₅]⁺. In distinct contrast, for the couple [Nb₂O₅]⁺/C₂H₆, one observes only single and double hydrogen‐atom abstraction from the hydrocarbon. DFT calculations reveal that different modes of attack in the initial phase of C?H bond activation together with quite different bond‐dissociation energies of the M?O bonds cause the rather varying reactivities of [V₂O₅]⁺ and [Nb₂O₅]⁺ towards ethane. The gas‐phase generation of acetaldehyde from ethane by bare [V₂O₅]⁺ may provide mechanistic insight in the related vanadium‐catalyzed large‐scale process.     

介孔分子筛MCM-41固载多氮杂环席夫碱与醋酸钴共同催化的Henry反应

采用2-苯基-2氢-1,2,3-三唑-4-醛固载改性的MCM-41与醋酸钴共同催化的Henry反应。通过傅里叶变换红外光谱(FT-IR)和X射线多晶衍射(XRD)等技术手段对催化剂进行了表征。在室温下考察了金属盐、溶剂对反应的影响,催化剂循环使用3次后催化活性基本无变化(产率可达80.5%)。     

强酸性阳离子交换树脂催化酯化丙烯酸和甲醇合成丙烯酸甲酯的反应动力学

以丙烯酸和甲醇为原料,强酸性阳离子交换树脂Amberlyst-15为催化剂,对苯二酚为阻聚剂,合成丙烯酸甲酯。 考察了醇酸摩尔比、催化剂用量和温度对反应过程的影响,在实验范围内,随着温度或者催化剂用量的增加,反应速率加快,丙烯酸的转化率也不断提高。 醇酸摩尔比的增加能提高丙烯酸的转化率,反应速率出现先增加后减缓的现象。 与此同时,建立该催化酯化反应的Pseudo-Homogeneous（PH）的理想和非理想以及Langmuir-Hinshelwood（LH）反应动力学模型,辨识得到相应反应动力学方程。 经比较,采用活度替代物质的量浓度的LH模型的平均相对偏差(MRD)最小,计算值为1.466%,最适合实际反应。     

Iridium‐Catalyzed Arylative Cyclization of Alkynones by 1,4‐Iridium Migration

1,4‐Metal migrations enable the remote functionalization of C? H bonds, and have been utilized in a wide variety of valuable synthetic methods. The vast majority of existing examples involve the 1,4‐migration of palladium or rhodium. Herein, the stereoselective synthesis of complex polycycles by the iridium‐catalyzed arylative cyclization of alkynones with arylboronic acids is described. To our knowledge, these reactions involve the first reported examples of 1,4‐iridium migration.     

Multisite Organic–Inorganic Hybrid Catalysts for the Direct Sustainable Synthesis of GABAergic Drugs

Multisite organic–inorganic hybrid catalysts have been prepared and applied in a new general, practical, and sustainable synthetic procedure toward industrially relevant GABA derivatives. The domino sequence is composed of seven chemical transformations which are performed in two one‐pot reactions. The method produces both enantiomeric forms of the product in high enantiopurity as well as the racemate in good yields after a single column purification step. This protocol highlights major process intensification, catalyst recyclability, and low waste generation.     

Palladium‐Catalyzed Decarboxylative Cycloaddition of Vinylethylene Carbonates with Formaldehyde: Enantioselective Construction of Tertiary Vinylglycols

An efficient method for the enantioselective construction of tertiary vinylglycols through a palladium‐catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with formaldehyde was developed. By using a palladium complex generated in situ from [Pd₂(dba)₃]?CHCl₃ and a phosphoramidite ligand as a catalyst under mild reaction conditions, the process allows conversion of racemic 4‐substituted 4‐vinyl‐1,3‐dioxolan‐2‐ones into the corresponding 1,3‐dioxolanes, as methylene acetal protected tertiary vinylglycols, in high yields with good to excellent enantioselectivities.     

Platinum‐Promoted Ga/Al2O3 as Highly Active,Selective, and Stable Catalyst for the Dehydrogenation of Propane

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga³⁺ species are the active species and where Pt functions as a promoter.