Electrocatalytic Hydrogenation of Pyridines and Other Nitrogen-Containing Aromatic Compounds.

The production of cyclic amines, which are vital to the pharmaceutical industry, relies on energy-intensive thermochemical hydrogenation. Herein, we demonstrate the electrocatalytic hydrogenation of nitrogen-containing aromatic compounds, specifically pyridine, at ambient temperature and pressure via a membrane electrode assembly with an anion-exchange membrane. We synthesized piperidine using a carbon-supported rhodium catalyst, achieving a current density of 25 mA cm-2 and a current efficiency of 99% under a circular flow until 5 F mol-1. Quantitative conversion of pyridine into piperidine with 98% yield was observed after passing 9 F mol-1, corresponding to 65% of current efficiency. The reduction of Rh oxides on the catalyst surface was crucial for catalysis. The Rh(0) surface interacts moderately with piperidine, decreasing the energy required for the rate-determining desorption step. The proposed process is applicable to other nitrogen-containing aromatic compounds and could be efficiently scaled up. This method presents clear advantages over traditional high-temperature and high-pressure thermochemical catalytic processes.

Wireless Electrochemical Gel Actuators.

Soft actuators generate motion in response to external stimuli and are indispensable for soft robots, particularly future miniature robots with complex structure and motion. Similarly to conventional hard robots, electricity is suitable for the stimulation. However, previous electrochemical soft actuators require a tethered connection to a power supply, limiting their size, structure, and motion. Here, wireless electrochemical soft actuators composed of hydrogels and driven by bipolar electrochemistry are reported. Viologen, which dimerizes by one-electron reduction and dissociates by one-electron oxidation, is incorporated in the side chains of the gel networks and works as a reversible cross-link. Wireless and reversible electrochemical actuation of the hydrogels, i.e., muscle-like shrinking and swelling, is demonstrated at microscopic and even macroscopic scales.

Additive-controlled chemoselective inter-/intramolecular hydroamination via electrochemical PCET process.

Electrochemically generated amidyl radical species produced distinct inter- or intramolecular hydroamination reaction products via a proton-coupled electron transfer (PCET) mechanism. Cyclic voltammetry (CV) analysis indicated that the chemoselectivity was derived from the size of the hydrogen bond complex, which consisted of the carbamate substrate and phosphate base, and could be controlled using 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as an additive. These results provide fundamental insights for the design of PCET-based redox reaction systems under electrochemical conditions.

Electrocatalytic hydrogenation of cyanoarenes, nitroarenes, quinolines, and pyridines under mild conditions with a proton-exchange membrane reactor.

An electrocatalytic hydrogenation of cyanoarenes, nitroarenes, quinolines, and pyridines using a proton-exchange membrane (PEM) reactor was developed. Cyanoarenes were then reduced to the corresponding benzylamines at room temperature in the presence of ethyl phosphate. The reduction of nitroarenes proceeded at room temperature, and a variety of anilines were obtained. The quinoline reduction was efficiently promoted by adding a catalytic amount of p-toluenesulfonic acid (PTSA) or pyridinium p-toluenesulfonate (PPTS). Pyridine was also reduced to piperidine in the presence of PTSA.

AC-Bipolar Electropolymerization of 3,4-Ethylenedioxythiophene in Ionic Liquids.

Recently, alternating current (AC)-bipolar electropolymerization of 3,4-ethylenedioxythiophene (EDOT) has been reported to produce poly(3,4-ethylenedioxythiophene) (PEDOT) fibers from the terminals of bipolar electrodes in acetonitrile solution (MeCN) containing low concentrations of supporting salts in a template-free manner. Here, we extend such methodology in ionic liquid (IL) media. Three kinds of ILs, diethylmethyl(2-methoxyethyl)ammonium tetrafluoroborate ([DEME][BF4]), 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), and diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide ([DEME][TFSI]), with different electric field transmission efficiencies and diffusion coefficients were employed as solvents for the AC-bipolar electropolymerization of EDOT. A variety of PEDOT morphologies were obtained in these three ILs, showing a relationship with the physicochemical properties of the ILs. We successfully confirmed the growth of PEDOT fibers in ILs and systematically discussed the factors that influenced their growth.

Synthesis, Structures, and Aggregation-Induced Emission Properties of Distyrylbenzene Derivatives Containing Fluorine Groups.

Distyrylbenzene derivatives with substituents on the vinylene moieties have been studied due to interest in their optoelectronic properties. In this study, we focused on distyrylbenzene derivatives with monofluoroolefin structures, expecting intermolecular H-F interactions in the solid state. UV-vis and fluorescence spectra of the obtained compounds were measured and compared with those of unsubstituted distyrylbenzene. The crystal structures of each compound were determined by single crystal X-ray diffraction and Hirshfeld surface analysis to understand the intermolecular contacts.

Oxidation Potential Gap (ΔEox ): The Hidden Parameter in Redox Chemistry.

Oxidative biaryl coupling of aryls with different electronic features generally fails. However, this has not been systematically studied via theoretical analysis, and thus, the crucial factor governing coupling efficiency remains unclear. Herein, we propose that the "oxidation potential gap (ΔEox )" is a key parameter in predicting the efficiency of an intramolecular oxidative coupling reaction, with ΔEox defined as a difference in the oxidation potentials of the relevant aromatic rings. Our experimental and computational analyses revealed that the efficiency of an aromatic intramolecular coupling reaction correlates with the activation energy (ΔE≠ ) of C-C bond formation of the radical cation intermediates. Furthermore, ΔE≠ correlates with ΔEox . Therefore, we demonstrate the tuning of ΔEox by attaching cleavable extra electron-donating/-withdrawing groups, enabling the rational synthesis of a phenanthridone skeleton using aromatic rings with an electronic gap.

Synthesis of piperidine and pyrrolidine derivatives by electroreductive cyclization of imine with terminal dihaloalkanes in a flow microreactor.

We have successfully synthesized piperidine and pyrrolidine derivatives by electroreductive cyclization using readily available imine and terminal dihaloalkanes in a flow microreactor. Reduction of the substrate imine on the cathode proceeded efficiently due to the large specific surface area of the microreactor. This method provided target compounds in good yields compared to a conventional batch-type reaction. Furthermore, piperidine and pyrrolidine derivatives could be obtained on preparative scale by continuous electrolysis for approximately 1 hour.

Electrosynthesis in Laminar Flow Using a Flow Microreactor.

Electrosynthesis and microflow synthesis have become essential tools in their own rights in modern organic synthesis. In this personal account, we summarize our works on the integrated use of these techniques, i. e., electrosynthesis in a flow microreactor. Our group has developed an electrochemical microflow system composed of a pair of electrodes that face each other to form a micrometer-scale gap for the flow path, through which solution passes in laminar flow. By the aid of laminar flow, unprecedented chemo- and electrochemical selectivity has been observed, which is not achievable with conventional batch-type electrochemical cells. In addition, we showcase various unique electrochemical systems and reactions achieved with the flow microreactor, including self-supported electrolysis, efficient paired electrolysis, in situ generation of active species and its flash use, the spaciotemporal control of electropolymerization, and combinatorial screening of the reaction conditions.

Integrated Flow Synthesis of α-Amino Acids by In Situ Generation of Aldimines and Subsequent Electrochemical Carboxylation.

The synthesis of α-amino acids was carried out in a continuous flow system. In this system, aldimines were efficiently generated in situ via the dehydration-condensation of aldehydes with anilines in a desiccant bed column filled with 4 Å molecular sieves desiccant, followed by reaction with CO2 in an electrochemical flow microreactor to afford the α-amino acids in high to moderate yields. The present system can provide α-amino acids without using stoichiometric amounts of metal reagents or highly toxic cyanide reagents.

Alkali Metal Fluorides in Fluorinated Alcohols: Fundamental Properties and Applications to Electrochemical Fluorination.

Fundamental properties of alkali metal fluorides (MF, M = Cs, K) dissolved in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) or in 3,3,3-trifluoroethanol (TFE) are investigated, including solubility, conductivity, and viscosity. Solid-state structures of single crystals obtained from CsF/HFIP and CsF/TFE are described for the first time, giving insights into the multiple interactions between fluorinated alcohols and CsF. Applications in electrochemical fluorination reactions are successfully demonstrated.

Electrocatalytic hydrogenation of benzoic acids in a proton-exchange membrane reactor.

The highly efficient chemoselective electrocatalytic hydrogenation of benzoic acids (BAs) to cyclohexanecarboxylic acids (CCAs) was carried out in a proton-exchange membrane reactor under mild conditions without hydrogenation of the carboxyl group. Among the investigated catalysts, the PtRu alloy catalyst was found to be the most suitable for achieving high current efficiencies for production of CCAs. An electrochemical spillover mechanism on the PtRu alloy catalyst was also proposed.

Fabrication of Gradient and Patterned Organic Thin Films by Bipolar Electrolytic Micelle Disruption Using Redox-Active Surfactants.

Bipolar electrochemistry could be regarded as a powerful approach for selective surface modification due to the beneficial feature that a wirelessly controllable potential distribution on bipolar electrodes (BPEs). Herein we report a bipolar electrolytic micelle disruption (BEMD) system for the preparation of shaped organic films. A U-shaped bipolar electrolytic system with a sigmoidal potential gradient on the BPE gave gradient-thin films including various interesting organic compounds, such as a polymerizable monomer, an organic pigment and aggregation induced emission (AIE) molecules. The gradient feature was characterized by UV-Vis absorption, thickness measurements and surface morphology analysis. Corresponding patterned films were also fabricated using a cylindrical bipolar electrolytic setup that enables site-selective application of the potential on the BPE. Such a facile BEMD approach will open a long-term perspective with respect to organic film preparation.

Bipolar Electrochemistry: A Powerful Tool for Electrifying Functional Material Synthesis.

Electrosynthesis is a powerful method for the synthesis of organic, inorganic, and polymeric materials based on electron-transfer-driven reactions at the substrate/electrode interface. The use of electricity for synthetic reactions without the need for hazardous chemical oxidants and reductants is recognized as a green and sustainable method. Other advantages include control of the reaction selectivity by tuning the electrode potentials. A different mode for driving electrochemical reactions has recently been proposed, in which bipolar electrodes (BPEs) are available as wireless electrodes that undergo anodic and cathodic reactions simultaneously. Bipolar electrochemistry is an old technology that has recently garnered renewed attention because of the interesting features of BPEs: (i) the wireless nature of a BPE is useful for sensors and material synthesis; (ii) the gradient potential distribution on BPEs is a powerful tool for the preparation of gradient surfaces and materials; and (iii) electrophoresis is available for effective electrolysis. In addition to these unique features, a BPE system only requires a small amount of supporting electrolyte in principle, whereas a large amount of electrolyte is necessary in conventional electrochemistry. Hence, bipolar electrochemistry is an inherently green and sustainable chemical process for the synthesis of materials. In this Account, recent progress in bipolar electrochemistry for the electrosynthesis of functional materials is summarized. The wireless nature of BPEs was utilized for symmetry breaking to produce anisotropic materials based on the site-selective modification of conductive objects by electrodeposition and electropolymerization. Potential gradients on a BPE interface have been successfully used as controllable templates to form molecular or polymeric gradient materials, which are potentially applicable for high throughput analytical equipment or as biomimetic materials. The electric field necessary to drive BPEs is also potentially useful to induce the directed migration of charged species. The synergetic effects of electrophoresis and electrolysis were also successfully demonstrated to obtain various functional materials. These features of bipolar electrochemistry and the various combinations of techniques have the potential to change the methodologies of material synthesis. Furthermore, the fundamental principle of bipolar electrochemistry infers that very small amounts of supporting electrolyte are necessary for an electrode system, which is expected to lead new methods of sustainable organic electrosynthesis.

Te-Li Exchange Reaction of Tellurophene-Containing π-Conjugated Polymer as Potential Synthetic Tool for Functional π-Conjugated Polymers.

On the basis of the facts that tellurophene-containing π-conjugated polymers are obtainable from organotitanium polymers and that the tellurium atoms in the tellurophene derivatives can be transformed into lithium atoms, the synthesis of reactive lithiated polymer precursor and its transformations into some functionalized π-conjugated polymers are described. A regioregular organometallic polymer having 1,4-dilithio-1,3-butadiene and 9,9-dioctylfluorene-2,7-diyl units is generated by the reaction of a tellurophene-containing polymer having the number-average molecular weight (Mn ) and molecular weight distribution (Mw /Mn ) of 5890 and 1.9, respectively, with n-butyllithium (2.4 equiv.) at -78 °C to -60 °C for 3 h. The lithiated polymer thus prepared is subjected to reactions with electrophiles to produce functionalized π-conjugated polymers. For example, a π-conjugated polymer possessing 1,4-bis(tri-n-butylstannyl)-1,3-butadiene-1,4-diyl unit is obtained in 67% yield by the reaction with tri-n-butyltin chloride (2.4 equiv.) at -60 °C to ambient temperature for 12 h in tetrahydrofuran, whose Mn and Mw /Mn are estimated as 7320 and 2.5, respectively, by size exclusion chromatography. The absorption maximum and onset of the obtained polymer are observed at 380 and 465 nm, respectively, in the UV-vis spectrum, from which the optical band gap of the polymer is estimated as 2.67 eV.

Synthesis of Ribo-Azanucleosides by Anodic Oxidation: Reactivity Control of Intermediate for Efficient Access to Pharmacophores.

Azanucleosides, the sugar-modified nucleoside analogues, have various biological activities, while their efficient synthetic strategy is still under development. Herein, a novel method for the synthesis of pharmaceutically relevant azanucleosides, ß-anomers of ribo-azanucleosides, by means of site-specific anodic C-H activation by using a nitroalkane-lithium perchlorate medium is reported. A mechanistic study of the electrochemical reaction and the armed/disarmed concept from traditional glycochemistry revealed that the 2'-substituent has a significant effect on the reactivity of prolinol derivative, and suitable carboxylic acid additives can control the reactivity of the intermediate species, an iminium cation equivalent. Finally, this method was demonstrated to be applicable for the synthesis of ß-anomers of ribo-azanucleosides with all four nucleobases in a stereoselective manner.