As two coexisting and fast-growing research fields in modern synthetic chemistry, the merging of organocatalysis and C–H bond functionalization is well foreseeable, and the joint force along this line has been demonstrated to be a powerful approach in making inert C–H bond functionalization more viable, predictable, and selective. In this review, we provide a comprehensive summary of organocatalysis in inert C–H bond functionalization over the past two decades. The review is arranged by types of inert C–H bonds including alkane C–H, arene C–H, and vinyl C–H as well as those activated benzylic C–H, allylic C–H, and C–H bonds alpha to the heteroatom such as nitrogen and oxygen. In each section, the discussion is classified by the explicit organocatalytic mode involved.

Organocatalysis in Inert C–H Bond Functionalization

The electrochemical CO2 reduction reaction (CO2 RR) to give C1 (formate and CO) products is one of the most techno-economically achievable strategies for alleviating CO2 emissions. Now, it is demonstrated that the SnOx shell in Sn2.7 Cu catalyst with a hierarchical Sn-Cu core can be reconstructed in situ under cathodic potentials of CO2 RR. The resulting Sn2.7 Cu catalyst achieves a high current density of 406.7±14.4 mA cm-2 with C1 Faradaic efficiency of 98.0±0.9 % at -0.70 V vs. RHE, and remains stable at 243.1±19.2 mA cm-2 with a C1 Faradaic efficiency of 99.0±0.5 % for 40 h at -0.55 V vs. RHE. DFT calculations indicate that the reconstructed Sn/SnOx interface facilitates formic acid production by optimizing binding of the reaction intermediate HCOO* while promotes Faradaic efficiency of C1 products by suppressing the competitive hydrogen evolution reaction, resulting in high Faradaic efficiency, current density, and stability of CO2 RR at low overpotentials.

In Situ Reconstruction of a Hierarchical Sn-Cu/SnOx Core/Shell Catalyst for High-Performance CO2 Electroreduction.

https://rua.ua.es/dspace/bitstream/10045/88608/5/2019_Beletskaya_etal_CoordChemRev_revised.pdf

The Suzuki-Miyaura reaction after the Nobel prize

As star material, perovskites have been widely used in the fields of optics, photovoltaics, electronics, magnetics, catalysis, sensing, etc. However, some inherent shortcomings, such as low efficiency (power conversion efficiency, external quantum efficiency, etc.) and poor stability (against water, oxygen, ultraviolet light, etc.), limit their practical applications. Downsizing the materials into nanostructures and incorporating rare earth (RE) ions are effective means to improve their properties and broaden their applications. This review will systematically summarize the key points in the design, synthesis, property improvements and application expansion of RE-containing (including both RE-based and RE-doped) halide and oxide perovskite nanomaterials (PNMs). The critical factors of incorporating RE elements into different perovskite structures and the rational design of functional materials will be discussed in detail. The advantages and disadvantages of different synthesis methods for PNMs will be reviewed. This paper will also summarize some practical experiences in selecting suitable RE elements and designing multi-functional materials according to the mechanisms and principles of REs promoting the properties of perovskites. At the end of this review, we will provide an outlook on the opportunities and challenges of RE-containing PNMs in various fields.

Rare-earth-containing perovskite nanomaterials: design, synthesis, properties and applications

Boron's unique position in the Periodic Table, that is, at the apex of the line separating metals and nonmetals, makes it highly versatile in chemical reactions and applications. Contemporary demand for renewable and clean energy as well as energy‐efficient products has seen boron playing key roles in energy‐related research, such as 1) activating and synthesizing energy‐rich small molecules, 2) storing chemical and electrical energy, and 3) converting electrical energy into light. These applications are fundamentally associated with boron's unique characteristics, such as its electron‐deficiency and the availability of an unoccupied p orbital, which allow the formation of a myriad of compounds with a wide range of chemical and physical properties. For example, boron's ability to achieve a full octet of electrons with four covalent bonds and a negative charge has led to the synthesis of a wide variety of borate anions of high chemical and electrochemical stability—in particular, weakly coordinating anions. This Review summarizes recent advances in the study of boron compounds for energy‐related processes and applications.

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Boron: Its Role in Energy-Related Processes and Applications.

Cover Picture: Continuous‐Flow Suzuki‐Miyaura and Mizoroki‐Heck Reactions under Microwave Heating Conditions (Chem. Rec. 1/2019)

This paper describes practical and selective hydrogenation methodologies using heterogeneous palladium catalysts. Chemoselectivity develops dependent on the catalyst activity based on the characteristic of the supports, derived from structural components, functional groups, and/or morphologies. We especially focus on our recent development of heterogeneous palladium catalysts supported on chelate resin, ceramic, and spherically shaped activated carbon. In addition, the application of flow technology for chemoselective hydrogenation using the palladium catalysts immobilized on molecular sieves 3A and boron nitride is outlined.

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Recent Development of Palladium-Supported Catalysts for Chemoselective Hydrogenation

A unique heterogeneous palladium catalyst (7% Pd/WA30) supported on an anion exchange resin, which contains N,N-dimethylaminoalkyl functionalities on the polymer backbone, was developed. 7% Pd/WA30 could smoothly catalyze Suzuki–Miyaura reaction of even less reactive heteroaryl chlorides and heteroaryl boronic acids to afford various (hetero)biaryls due to the electron-donating effect of the tert-amines on WA30 to Pd species. It was also applicable as a chemoselective hydrogenation catalyst, showing inactivity for the hydorogenolysis of tert-butyldimethylsilyl (TBS) ethers, alkyl benzyl ethers, and benzyl alcohols. The tert-amines on WA30 acted as moderate catalyst poisons for Pd, resulting in chemoselective hydrogenation. 7% Pd/WA30 was reused for at least five times without any loss of the hydrogenation catalytic activity.

Development of a Unique Heterogeneous Palladium Catalyst for the Suzuki–Miyaura Reaction using (Hetero)aryl Chlorides and Chemoselective Hydrogenation

In the presence of palladium on carbon (Pd/C) as a catalyst, hydrogenation of aliphatic nitriles in cyclohexane efficiently proceeded at 25–60 °C under ordinary hydrogen gas pressure to afford the corresponding tertiary amines. However, the use of rhodium on carbon (Rh/C) led to the highly selective generation of secondary amines. Hydrogenation of aromatic nitriles and cyclohexanecarbonitrile selectively produced secondary amines in the presence of either Pd/C or Rh/C.

Tomohiro Ichikawa

Papers

Cover Picture: Continuous‐Flow Suzuki‐Miyaura and Mizoroki‐Heck Reactions under Microwave Heating Conditions (Chem. Rec. 1/2019)

Recent Development of Palladium-Supported Catalysts for Chemoselective Hydrogenation

Development of a Unique Heterogeneous Palladium Catalyst for the Suzuki–Miyaura Reaction using (Hetero)aryl Chlorides and Chemoselective Hydrogenation

Catalyst-Dependent Selective Hydrogenation of Nitriles: Selective Synthesis of Tertiary and Secondary Amines

Selective Synthesis of Primary Amines from Nitriles under Hydrogenation Conditions