Carbohydrate-based nanostructured catalysts: applications in organic transformations

The requirement of green and sustainable materials to prepare heterogeneous catalysts has intensified for practical reasons over the past few decades. Carbohydrates are possibly the most plentiful and renewable organic materials in nature with inimitable physiochemical properties, plausible low-cost and large-scale production, and sustainability features could be exploited in the generation of nanostructured heterogeneous catalysts. This review article outlines the organic transformations catalyzed by diverse carbohydrate-based nanostructured catalysts in greener and environmentally friendly processes. Selected examples are highlighted for a variety of organic reactions exploiting the proposed catalysts’ reactivity and reusability, and interactions with the intrinsic nature of the applied carbohydrate supports; advantages and speculated challenges of the introduced catalysts are deliberated as well.     

金属衬底在石墨烯化学气相沉积生长中的作用

以过渡金属为催化衬底的化学气相沉积法(Chemical Vapor Deposition，CVD)已经可以制备与机械剥离样品相媲美的石墨烯，是实现石墨烯工业应用的关键技术之一。原子尺度理论研究能够帮助我们深刻理解石墨烯生长机理，为实验现象提供合理的解释，并有可能成为将来实验设计的理论指导。本文从理论计算的角度，总结了各种金属衬底在石墨烯CVD生长过程中的各种作用与相应的机理，包括在催化碳源裂解、降低石墨烯成核密度等，催化加快石墨烯快速生长，修复石墨烯生长过程中产生的缺陷，控制外延生长石墨烯的晶格取向，以及在降温过程中石墨烯褶皱与金属表面台阶束的形成过程等。在本文最后，我们对当前石墨烯生长领域中亟需解决的理论问题进行了深入探讨与展望。     

Design of Functional Carbon Composite Materials for Energy Conversion and Storage

The carbon composite materials have been a research hotspot in the fields of catalysis, energy conversion and so on, because of their features of large structure and morphology variety, good chemical and electrochemical stability, and high electronic conductivity, large specific surface area and rich active sites. This paper summarizes some research progress of carbon composite materials, including assembly methodologies, their structure regulation, properties, and related applications. Moreover, the current challenges and the prospects of these materials are also discussed.     

Recent advances in the application of nanoparticles in the selective reduction of carbon–carbon double bonds

Herein, we present recent advances in the application of metal nanoparticles in the selective hydrogenation of C–C double bonds. The review focuses on reduction methods of alkenes, arenes, and aromatic heterocycles, which were classified according to transition metals used as catalysts. The majority of described systems concern direct hydrogenation, which is of particular importance to industrial processes. Nonetheless, interesting transfer hydrogenation protocols were also developed, which may be incredibly convenient for laboratory purposes. Some of the methods are distinguished with excellent chemoselectivity making them the perfect tool for the synthesis of compounds containing reducible functional groups. Apart from noble metals, the application of earth-abundant ones as catalysts was a subject of studies, and the related methods were highlighted.     

Alkyne–azide cycloaddition catalyzed by a dinuclear copper(I) complex

A novel dinuclear copper complex Cu^I₂(pip)₂ was used as a catalyst for alkyne–azide cycloaddition (CuAAC) reaction. High yields (95–99%) were obtained for various substrates at a low loading of 0.2 mol %. The unique structure, high stability of the dinuclear structure in solution, and easy preparation make this complex not only a high-efficiency catalyst but also a model for understanding the mechanism of the CuAAC reaction.     

Oxidation and Reduction Pathways in the Knowles Hydroamination via a Photoredox-Catalyzed Radical Reaction**

Systematic reaction path exploration revealed the entire mechanism of Knowles's light-promoted catalytic intramolecular hydroamination. Bond formation/cleavage competes with single electron transfer (SET) between the catalyst and substrate. These processes are described by adiabatic processes through transition states in an electronic state and non-radiative transitions through the seam of crossings (SX) between different electronic states. This study determined the energetically favorable SET path by introducing a practical computational model representing SET as non-adiabatic transitions via SXs between substrate's potential energy surfaces for different charge states adjusted based on the catalyst's redox potential. Calculations showed that the reduction and proton shuttle process proceeded concertedly. Also, the relative importance of SET paths (giving the product and leading back to the reactant) varies depending on the catalyst's redox potential, affecting the yield.     

Temperature-Controlled Mechanochemistry Unlocks the Nickel-Catalyzed Suzuki–Miyaura-Type Coupling of Aryl Sulfamates at Different Scales

Several mechanochemically heated processes have been published in recent years. However, precise control over the mechanochemical catalysed coupling reactions remained elusive. A recent report from Leitch, Browne and co-workers demonstrated how a programmable jar heater manifold delivers an efficient methodology for the Suzuki–Miyaura-type cross coupling reaction of aryl sulfamates and aryl boronic acid species. This methodology can be readily upscaled 200-fold using twin-screw extrusion methodologies.     

Enantioselective Hydrosilylation of β,β-Disubstituted Enamides to Construct α-Aminosilanes with Vicinal Stereocenters

Despite the advances in the area of catalytic alkene hydrosilylation, the enantioselective hydrosilylation of alkenes bearing a heteroatom substituent is scarce. Here we report a rhodium-catalyzed hydrosilylation of β,β-disubstituted enamides to directly afford valuable α-aminosilanes in a highly regio-, diastereo-, and enantioselective manner. Stereodivergent synthesis could be achieved by regulating substrate geometry and ligand configuration to generate all the possible stereoisomers in high enantio-purity.