Geminal frustrated Lewis pairs (FLPs) are expected to exhibit increased reactivity when the donor and acceptor sites are perfectly aligned. This is shown for reactions of the nonfluorinated FLP tBu(2)PCH(2)BPh(2) with H(2), CO(2), and isocyanates and supported computationally.

The use of water as an oxygen and hydrogen source for the paired oxygenation and hydrogenation of organic substrates to produce valuable chemicals is of utmost importance as a means of establishing green chemical syntheses. Inspired by the active Ni 3+ intermediates involved in electrocatalytic water oxidation by nickel‐based materials, we prepared NiB x as a catalyst and used water as the oxygen source for the oxygenation of various organic compounds. NiB x was further employed as both an anode and a cathode in a paired electrosynthesis cell for the respective oxygenation and hydrogenation of organic compounds, with water as both the oxygen and hydrogen source. Conversion efficiency and selectivity of ≥99 % were observed during the oxygenation of 5‐hydroxymethylfurfural to 2,5‐furandicarboxylic acid and the simultaneous hydrogenation of p ‐nitrophenol to p ‐aminophenol. This paired electrosynthesis cell has also been coupled to a solar cell as a stand‐alone reactor in response to sunlight.

Low-cost transition metal-based electrocatalysts for water oxidation and understanding their structure−activity relationship are greatly desired for clean and sustainable chemical fuel production. Herein, a core− shell (CS) NiFeCr metal/metal hydroxide catalyst was fabricated on a 3D Cu nanoarray by a simple electrodeposition−activation method. A synergistic promotion effect between electronic structure modulation and nanostructure regulation was presented on a CS-NiFeCr oxygen evolution reaction (OER) catalyst: the 3D nanoarchitecture facilitates the mass transport process, the in situ formed interface metal/metal hydroxide heterojunction accelerates the electron transfer, and the electronic structure modulation by Cr incorporation improves the reaction kinetics. Benefiting from the synergy between structural and electronic modulation, the catalyst shows excellent activity toward water oxidation under alkaline conditions: overpotential of 200 mV at 10 mA/cm 2 current density and Tafel slope of 28 mV/dec. This work opens up a new window for understanding the structure−activity relationship of OER catalysts and encourages new strategies for development of more advanced OER catalysts.

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E=MCR2! The introduction of orthogonal functional groups in multicomponent reactions (MCRs) with unique solvent and functional‐group compatibility enables their combination with other multicomponent reactions in one pot. The resulting novel 5‐ and 6CRs and an unprecedented 8CR afford very complex products in up to 80 % yields (see picture), with up to nine new bond formations and eleven diversity points in a single reaction.

An enantioselective synthesis of an intermediate in the Tanino total synthesis of solanoeclepin A has been developed. The key step was an intramolecular [2+2] photocycloaddition, which led to the tricyclo[5.2.1.0(1, 6)] decane core in six steps. The first photosubstrate, prepared through an indium-mediated Barbier-type reaction, gave an excellent [2+2] cycloaddition, but it could not be obtained in sufficient enantiopurity. The second photosubstrate, prepared through an asymmetric allene diborylation in high enantiomeric excess, gave the [2+2] cycloaddition product in high yield on irradiation at 365 nm on 20 g scale in a flow system. Other important steps were the replacement of a boronate group at the quaternary carbon by a vinyl group and diastereoselective cyclopropanation of an allylic alcohol.

Molecular catalysts possess numerous advantages over conventional heterogeneous catalysts in precise structure regulation, indepth mechanism understanding, and efficient metal utilization. Various molecular catalysts have been reported that efficiently catalyze reactions involved in artificial photosynthesis, however, these catalysts have been rarely considered in view of practical applications. With this review, firstly we demonstrate in the introduction that molecular catalysts can bring new opportunities to proton exchange membrane (PEM) electrolyzers. In the following parts, we provide an overview of molecular catalyst modified carbon materials developed for electrochemical water oxidation, proton reduction, and CO 2 reduction reactions. These materials and the involved immobilization strategies as well as characterization techniques may be directly employed in the investigations of application of molecular catalysts in PEM electrolyzers. The future scientific perspectives and challenges to advance this promising, yet underdeveloped technology for solar fuel production, integrating PEM electrolyzer with molecular-level catalysis, are discussed in the conclusions.

Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.