Asymmetric Organocatalytic Cyclization and Cycloaddition Reactions

In heterogeneous single-metal-site catalysts (HSMSCs) the active metal centres are located individually on a support and are stabilized by neighbouring surface atoms such as nitrogen, oxygen or sulfur. Modern characterization techniques allow the identification of these individual metal atoms on a given support, and the resulting materials are often referred as single-atom catalysts. Their electronic properties and catalytic activity are tuned by the interaction between the central metal and the neighbouring surface atoms, and their atomically dispersed nature allows for metal utilization of up to 100%. In this way, HSMSCs provide new opportunities for catalysis, and with respect to structure build a bridge between homogeneous and heterogeneous catalysis. Herein, selected publications from 2010 in this area are reviewed and their perspectives for the near future are highlighted. Where appropriate, comparisons between HSMSCs and homogeneous/heterogeneous counterparts are presented. Single-atom catalysts have drawn increasing attention as methods for their preparation and characterization improve. Here, Beller and co-workers discuss the latest developments in the field of single-metal-site catalysts, discussing how this catalyst class bridges heterogeneous and homogeneous catalysis, and providing a perspective on how the field might continue to develop.

Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts

In this review, a brief survey is offered on the main nanotechnology synthetic approaches available to heterogeneous catalysis, and a few examples are provided of their usefulness for such applications. We start by discussing the use of colloidal, reverse micelle, and dendrimer chemistry in the production of active metal and metal oxide nanoparticles with well-defined sizes, shapes, and compositions, as a way to control the surface atomic ensembles available for selective catalysis. Next we introduce the use of sol–gel and atomic layer deposition chemistry for the production and modification of high-surface-area supports and active phases. Reference is then made to the more complex active sites that can be created or carved on such supports by using organic structure-directing agents. We follow with an examination of the ability to achieve multiple functionality in catalysis via the design of dumbbells, core@shell, and other complex nanostructures. Finally, we consider the mixed molecular-nanostructure approach that can be used to develop more demanding catalytic sites, by derivatizing the surface of solids or tethering or immobilizing homogeneous catalysts or other chemical functionalities. We conclude with a personal and critical perspective on the importance of fully exploiting the synergies between nanotechnology and surface science to optimize the search for new catalysts and catalytic processes.

Nanostructured materials for applications in heterogeneous catalysis

The incorporation of a synthetic, catalytically competent metallocofactor into a protein scaffold to generate an artificial metalloenzyme (ArM) has been explored since the late 1970’s. Progress in the ensuing years was limited by the tools available for both organometallic synthesis and protein engineering. Advances in both of these areas, combined with increased appreciation of the potential benefits of combining attractive features of both homogeneous catalysis and enzymatic catalysis, led to a resurgence of interest in ArMs starting in the early 2000’s. Perhaps the most intriguing of potential ArM properties is their ability to endow homogeneous catalysts with a genetic memory. Indeed, incorporating a homogeneous catalyst into a genetically encoded scaffold offers the opportunity to improve ArM performance by directed evolution. This capability could, in turn, lead to improvements in ArM efficiency similar to those obtained for natural enzymes, providing systems suitable for practical applications and ...

/pdf/artificial-metalloenzymes-reaction-scope-and-optimization-2fb45ld2i6.pdf

Artificial Metalloenzymes: Reaction Scope and Optimization Strategies.

2.6.4. Other Carbohydrate-Based Catalysts 3976 2.7. Carbocyclic Ketones 3977 2.8. Ketones with an Attached Chiral Moiety 3979 3. Chiral Iminium Salt-Catalyzed Epoxidation 3979 3.

Organocatalytic Oxidation. Asymmetric Epoxidation of Olefins Catalyzed by Chiral Ketones and Iminium Salts

Laboratory for Advanced Materials and New Catalysis, School of Chemistry and Materials Science, Hubei University, Wuhan 430062, China,Laboratory of Natural Gas Utilization and Applied Catalysis, Dalian Institute of Chemical Physics of Chinese Academy of Sciences, Dalian 116023,China, and Jingmen Technological College, Jingmen 448000, ChinaReceived June 30, 2004

Advances in Homogeneous and Heterogeneous Catalytic Asymmetric Epoxidation

Synthesis of 3‐aminoalkyl‐2‐arylaminoquiazolin‐4(3H)‐ones and 3,3′‐disubstituted bis‐2‐arylaminoquinazolin‐4(3H)‐ones via reactions of 1‐aryl‐3‐(2‐ethoxycarbonylphenyl)carbodiimides with diamines

In recent years, covalent organic frameworks (COFs) have attracted enormous interest as a new generation of proton-exchange membranes, chemical sensors and electronic devices. However, to design high proton conductivity COFs, especially those with stimulus responsive performance remains a great challenge. Here, the first example of a light/heat switchable COF (COF-HNU9) has been synthesized by grafting a donor–acceptor Stenhouse adduct (DASA) within the channels of a β-ketoenamine-based COF. DASA groups in the nanopores of COF-HNU9 undergo a reversible open–closed photoisomerization upon visible light irradiation and are recovered by heating. Thus, COF-HNU9 exhibits not only a remarkably high proton conductivity, but also a highly effective switching performance. Under visible light irradiation at 98% RH, the proton conductivity of COF-HNU9 increases by three orders of magnitude at 25 °C and is up to 0.02 S cm−1 at 80 °C. Furthermore, the proton conductivity does not display any significant decrease even after 20 switching cycles. These results have been rationalized by a Grotthuss-type mechanism and verified by DFT calculations. The stimuli-responsive COF is conceptually confirmed by an optical control device with the light/heat switching proton conductive COF-HNU9 film, which is able to remote-control the illumination and switching off of an LED lamp without any current amplifier.

/pdf/a-visible-light-heat-responsive-covalent-organic-framework-3mcdqrxs.pdf

A visible light/heat responsive covalent organic framework for highly efficient and switchable proton conductivity

Regulating the Pore Microenvironment of Microporous Metal–Organic Frameworks for Efficient Adsorption of Low-Concentration Ammonia

Boron dipyrromethene (also known as bodipy), as a class of versatile and robust fluorophores and a structural analogue of porphyrins, has received a great deal of interests in the field of light-harvesting and energy-transfer processes. However, the fabrication of bodipy monomers into metal-organic frameworks (MOFs) and the exploitation of their potential still lags behind the porphyrin MOFs. In this work, two bodipy-based MOFs, BMOF 1D with 1D chain structure and BMOF 2D with 2D layer structure, were assembled by using dicarboxyl-functionalized bodipy ligands. BMOF 1D can also be converted to BMOF 2D by inserting additional ligands into BMOF 1D to cross-link the adjacent chains into the rhombic grid layer. During this process, spontaneous exfoliation occurred simultaneously and resulted in the formation of several hundred nanometer thickness BMOF 2D (nBMOF 2D), which can be further exfoliated into one-layer MOF nanosheets (BMON 2D) by using the ultrasonic liquid exfoliation method in a high yield. Featuring the distinct bodipy scaffolds in the porous frameworks, both BMOF 2D and BMON 2D displayed high reactivity and recyclability in the photocatalytic inverse hydroboration and cross-dehydrogenative coupling reactions to afford α-amino organoborons and α-amino amides in moderate to high yields. This work not only highlights the cascade utilization of ligand installation and ultrasonic liquid exfoliation methods to provide the single-layer MOF sheets in high yields but also advances the bodipy-based MOFs as a new type of heterogeneous photocatalysts in the forging of C-B and C-C bonds driven by visible light.

Bodipy-Based Metal-Organic Frameworks Transformed in Solid States from 1D Chains to 2D Layer Structures as Efficient Visible Light Heterogeneous Photocatalysts for Forging C-B and C-C Bonds.

Qing-Hua Xia

Papers

Advances in Homogeneous and Heterogeneous Catalytic Asymmetric Epoxidation

Synthesis of 3‐aminoalkyl‐2‐arylaminoquiazolin‐4(3H)‐ones and 3,3′‐disubstituted bis‐2‐arylaminoquinazolin‐4(3H)‐ones via reactions of 1‐aryl‐3‐(2‐ethoxycarbonylphenyl)carbodiimides with diamines

A visible light/heat responsive covalent organic framework for highly efficient and switchable proton conductivity

Regulating the Pore Microenvironment of Microporous Metal–Organic Frameworks for Efficient Adsorption of Low-Concentration Ammonia

Bodipy-Based Metal-Organic Frameworks Transformed in Solid States from 1D Chains to 2D Layer Structures as Efficient Visible Light Heterogeneous Photocatalysts for Forging C-B and C-C Bonds.