Recent progress in cathodic reduction-enabled organic electrosynthesis: Trends, challenges, and opportunities

Herein, a facile and general electroreductive deuteration of unactivated alkyl halides (X = Cl, Br, I) or pseudo-halides (X = OMs) using D2O as the economical deuterium source was reported. In addition to primary and secondary alkyl halides, sterically hindered tertiary chlorides also work very well, affording the target deuterodehalogenated products with excellent efficiency and deuterium incorporation. More than 60 examples are provided, including late-stage dehalogenative deuteration of natural products, pharmaceuticals, and their derivatives, all with excellent deuterium incorporation (up to 99% D), demonstrating the potential utility of the developed method in organic synthesis. Furthermore, the method does not require external catalysts and tolerates high current, showing possible use in industrial applications. 

/pdf/facile-and-general-electrochemical-deuteration-of-2zx3yc34.pdf

Facile and general electrochemical deuteration of unactivated alkyl halides

Herein, an efficient and facile approach to valuable β -hydroxy acid derivatives from readily available aryl epoxides and CO 2 with high chemo- and regioselectivity under mild and sustainable electrochemical conditions is described. This approach showed broad substrate scope and good functional-group compatibility. In addition to aryl epoxides, four- to six-membered aryl cyclic ethers could all be tolerated in the reaction to provide synthetically useful hydroxy acids with high efficiency. Further late-stage carboxylation of complex molecules and drug derivatives demonstrated its potential application in the pharmaceutical industry. Mechanistic studies disclosed possible reaction pathways.

Electrocarboxylation of Aryl Epoxides with CO2 for the Facile and Selective Synthesis of β-Hydroxy Acids.

Carbon dioxide (CO 2 ) is an abundant, inexpensive, renewable C1 resource and the main component of greenhouse gas, thereby the research for its sustainable and efficient conversion has received notable attention in recent years. Electrochemical organic synthesis, as a green and efficient synthetic method, is convinced to be an ideal approach for CO 2 utilization. In this review, recent advances in electrocarboxylation with CO 2 were summarized through different reaction types, which would disclose the great potential of electrocarboxylation in green organic synthesis.

Recent Advances in Electrocarboxylation with CO2.

Organic electrosynthesis is a green strategy for the synthesis of valuable molecules. Electrochemical reactions using sacrificial metal anodes enable new reactivity to be uncovered that could not be achieved with traditional non-electrochemical methods. Compared with reactions using metal powder as the reducing reagent, the mild electroreduction protocols usually exhibit diverse reactivity and excellent selectivity. The inexpensive metal anodes possess low oxidation potential, which could prevent undesired overoxidation of substrates, active intermediates and products. The in situ generated metal ions from sacrificial anodes could not only serve as Lewis acids to activate the reactants but also as a promoter or mediator. This tutorial review highlights the recent achievements in this rapidly growing area within the past five years. The sacrificial anode-enabled electroreductions are discussed according to the reaction type.

A guide to organic electroreduction using sacrificial anodes.

Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO2 has been demonstrated as a promising synthetic method. However, dicarboxylation of C─C single bonds with CO2 has rarely been investigated. Herein we report a novel electrochemical ring-opening dicarboxylation of C─C single bonds in strained rings with CO2. Structurally diverse glutaric acid and adipic acid derivatives were synthesized from substituted cyclopropanes and cyclobutanes in moderate to high yields. In contrast to oxidative ring openings, this is also the first realization of an electroreductive ring-opening reaction of strained rings, including commercialized ones. Control experiments suggested that radical anions and carbanions might be the key intermediates in this reaction. Moreover, this process features high step and atom economy, mild reaction conditions (1 atm, room temperature), good chemoselectivity and functional group tolerance, low electrolyte concentration, and easy derivatization of the products. Furthermore, we conducted polymerization of the corresponding diesters with diols to obtain a potential UV-shielding material with a self-healing function and a fluorine-containing polyester, whose performance tests showed promising applications.

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon-Carbon Single Bonds with CO2: Facile Synthesis of Diacids and Derivatization into Polyesters.

Dynamic covalent chemistry offers a solution to tackle the recycling issue of epoxy resins (EPs) and their carbon fiber-reinforced composites; however, the vulnerability to creep associated with the inflammable nature of the EPs are the key obstacles for their applications. Herein, we propose a feasible and facile strategy to overcome these obstacles by incorporating phosphorus-influenced Diels-Alder (DA) chemistry to construct dynamic epoxy networks. In the strategy, the electron-withdrawing phosphonate in the dienophile maleimide greatly promotes the thermal stability of the DA reaction, exhibiting excellent creep resistance, repairability, and malleability; while its flame-retardant activity improves the fire safety of the resultant thermosets. Meanwhile, nondestructive recycling of carbon fiber is achieved. The ease with which EP and its composites can be manufactured, used, recycled and re-used–without losing service performance–points to new orientation in sustainable composites. 

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/eom2.12388

Phosphonate‐influenced Diels‐Alder chemistry toward multi‐path recyclable, fire safe thermoset and its carbon fiber composites

Marine composites with antimicrobial fouling and fireproofing are indispensable for ocean facilities that resist extremely harsh environments. Marine life has excited various inspirations to withstand harsh environments, in which sandcastle worms secrete unique adhesives for gluing sand and shell fragments together to build robust and protective habitats. Herein, we design an adherable macromolecule interface containing tyramine and ammonium phosphate motifs to create superhighly flame-retardant and excellent antibacterial functional composites. The results demonstrate that the phenolic hydroxyl groups in tyramine improve the chemical affinity among ammonium polyphosphate, vinyl ester resin, and carbon fibers due to the great adhesion, while also exhibiting excellent broad-spectrum antimicrobial fouling properties for bacteria, mold, and algae. The tyramine and ammonium phosphate groups synergistically achieve superhigh fire-safety performance beyond current levels to powerfully defend human life in maritime confined spaces. This sandcastle-worm-inspired strategy emerges as an attractive candidate for super antimicrobial fouling and fireproof protection in extremely harsh ocean environments. 

A Sandcastle-Worm-Inspired Strategy toward Antimicrobial Fouling and Fireproof Composite

To ameliorate the inherent deficiencies of epoxy resins (EP) and to achieve flame-retardant EP with comprehensive performance for versatile applications, a phosphorus-containing polyester named PEDP with rigid-flexible spacers and bis-phosphaphenanthrene pendants was designed, prepared and successfully applied to EP as polymeric flame retardant with multifunctionalities. The obtained EP-PEDP thermosets did not show phase separation to achieve a high dispersion of PEDP and enhanced interaction between two components, which effectively improved the mechanical properties of the thermosets. EP-PEDP displayed excellent toughness, with impact toughness, fracture toughness KIC and GIC reaching 30.9 kJ·m−2, 1.27 MPa·m1/2 and 0.67 kJ·m−2, respectively, showing 166.4 %, 28.3 %, and 59.5 % greater than neat EP; yet tensile and flexural strength also increased rather than sacrificed. The combined flame-retardant action of PEDP in gaseous and condensed phases effectively improved the self-extinguishment and greatly suppressed the release of smoke and heat during burning to achieve high fire safety of EP-PEDP. In addition, EP-PEDP also possessed high glass transition temperature, satisfactory thermal stability, transparency with UV shielding capacity, as well as good dielectric and thermomechanical properties. The design and synthesis of this multifunctional phosphorus-containing polyester with a rigid-flexible integrated nature, which integrates mechanical enhancement, serves as a promising polymeric flame retardant for high-performance EP to meet diverse requirements. 

A rigid-flexible integrated polyester with bis-phosphaphenanthrene pendants towards simultaneously flame-retarded and toughened epoxy resins with multifunctionalities

2D@0D Multidimensional Nanoparticles for Improving the Fire Safety of Epoxy Resin

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