Photosynthetic biohybrid coculture for tandem and tunable CO2 and N2 fixation.

Solar-driven bioelectrosynthesis represents a promising approach for converting abundant resources into value-added chemicals with renewable energy. Microorganisms powered by electrochemical reducing equivalents assimilate CO2, H2O, and N2 building blocks. However, products from autotrophic whole-cell biocatalysts are limited. Furthermore, biocatalysts tasked with N2 reduction are constrained by simultaneous energy-intensive autotrophy. To overcome these challenges, we designed a biohybrid coculture for tandem and tunable CO2 and N2 fixation to value-added products, allowing the different species to distribute bioconversion steps and reduce the individual metabolic burden. This consortium involves acetogen Sporomusa ovata, which reduces CO2 to acetate, and diazotrophic Rhodopseudomonas palustris, which uses the acetate both to fuel N2 fixation and for the generation of a biopolyester. We demonstrate that the coculture platform provides a robust ecosystem for continuous CO2 and N2 fixation, and its outputs are directed by substrate gas composition. Moreover, we show the ability to support the coculture on a high-surface area silicon nanowire cathodic platform. The biohybrid coculture achieved peak faradaic efficiencies of 100, 19.1, and 6.3% for acetate, nitrogen in biomass, and ammonia, respectively, while maintaining product tunability. Finally, we established full solar to chemical conversion driven by a photovoltaic device, resulting in solar to chemical efficiencies of 1.78, 0.51, and 0.08% for acetate, nitrogenous biomass, and ammonia, correspondingly. Ultimately, our work demonstrates the ability to employ and electrochemically manipulate bacterial communities on demand to expand the suite of CO2 and N2 bioelectrosynthesis products.

Convergent total synthesis of (+)-calcipotriol: A scalable, modular approach to vitamin D analogs.

A convergent approach for the total synthesis of calcipotriol (brand name: Dovonex), a proven vitamin D analog used for the treatment of psoriasis, and medicinally relevant synthetic analogs is described. A complete approach, not wedded to semisynthesis, toward both the A-ring and CD-ring is reported. From a retrosynthetic standpoint, hidden symmetry within the decorated A-ring is disclosed, which allowed for scalable quantities of this advanced intermediate. In addition, a radical retrosynthetic approach is described, which highlights an electrochemical reductive coupling as well as an intramolecular hydrogen atom transfer Giese addition to establish the 6,5-transcarbon skeleton found in the vitamin D family. Finally, a late-stage decarboxylative cross-coupling approach allowed for the facile preparation of various C20-arylated derivatives that show promising biological activity in an initial bioassay.

Membrane-Free Selective Semi-Hydrogenation of Alkynes Over an In Situ Formed Copper Nanoparticle Electrode.

Selective semi-hydrogenation of alkynes is a significant reaction for preparing functionalized alkenes. Electrochemical semi-hydrogenation presents a sustainable alternative to the traditional thermal process. In this research, affordable copper acetylacetonate is employed as a catalyst precursor for the electrocatalytic hydrogenation of alkynes, using MeOH as the hydrogen source in an undivided cell. Good to excellent yields for both aromatic and aliphatic internal/terminal alkynes are obtained under constant current conditions. Notably, up to 99% Z selectivity is achieved for various internal alkynes. Mechanistic investigations revealed the formation of copper nanoparticles (NPs) at the cathode during electrolysis, acting as the catalyst for the selective semireduction of alkynes. The copper NPs deposited cathode demonstrated reusable for further hydrogenation.

Defect Engineering of 2D Copper Tin Composite Nanosheets Realizing Promoted Electrosynthesis Performance of Hydrogen Peroxide.

The transformation of the two-electron oxygen reduction reaction (2e-ORR) to produce hydrogen peroxide (H2 O2 ) is a promising green synthesis approach that can replace the high-energy consumption anthraquinone process. However, designing and fabricating low-cost, non-precious metal electrocatalysts for 2e-ORR remains a challenge. In this study, a method of combining complexation precipitation and thermal treatment to synthesize 2D copper-tin composite nanosheets to serve as the 2e-ORR electrocatalysts is utilized, achieving a high H2 O2 selectivity of 92.8% in 0.1 m KOH, and a bulk H2 O2 electrosynthesis yield of 1436 mmol·gcat -1 ·h-1 using a flow cell device. Remarkably, the H2 O2 selectivity of this catalyst decreases by only 0.5% after 10,000 cyclic voltammetry (CV) cycles. In addition, it demonstrates that the same catalyst can achieve 97% removal of the organic pollutant methyl blue in an aqueous system solution within 1 h using the on-site degradation technology. A reasonable control of defect concentration on the 2D copper-tin composite nanosheets that can effectively improve the electrocatalytic performance is found. Density functional theory calculations confirm that the surface of the 2D copper-tin composite nanosheets is conducive to the adsorption of the key intermediate OOH* , highlighting its excellent electrocatalytic performance for ORR with high H2 O2 selectivity.

Tuning Main Group Element-based Metal-Organic Framework to Boost Electrocatalytic Nitrogen Reduction Under Ambient Conditions.

Main group element-based materials are emerging catalysts for ammonia (NH3 ) production via a sustainable electrochemical nitrogen reduction reaction (N2 RR) pathway under ambient conditions. However, their N2 RR performances are less explored due to the limited active behavior and unclear mechanism. Here, an aluminum-based defective metal-organic framework (MOF), aluminum-fumarate (Al-Fum), is investigated. As a proof of concept, the pristine Al-Fum MOF is synthesized by the solvothermal reaction process, and the defect engineering method namely solvent-assisted linker exchange, is applied to create the defective Al sites. The defective Al sites play an important role in ensuring the N2 RR activity for defective Al-Fum. It is found that only the defective Al-Fum enables stable and effective electrochemical N2 RR, in terms of the highest production rate of 53.9 µg(NH3 ) h-1 mgcat -1 (in 0.4 m K2 SO4 ) and the Faradaic efficiency of 73.8% (in 0.1 m K2 SO4 ) at -0.15 V vs reversible hydrogen electrode) under ambient conditions. Density functional theory calculations confirm that the N2 activation can be achieved on the defective Al sites. Such sites also allow the subsequent protonation process via the alternating associative mechanism. This defect characteristic gives the main group Al-based MOFs the ability to serve as promising electrocatalysts for N2 RR and other attractive applications.

Boron-Doped Ti3C2Tx MXene for Effective and Durable High-Current-Density Ammonia Synthesis.

Ammonia (NH3) synthesis via the nitrate reduction reaction (NO3RR) offers a competitive strategy for nitrogen cycling and carbon neutrality; however, this is hindered by the poor NO3RR performance under high current density. Herein, it is shown that boron-doped Ti3C2Tx MXene nanosheets can highly efficiently catalyze the conversion of NO3RR-to-NH3 at ambient conditions, showing a maximal NH3 Faradic efficiency of 91% with a peak yield rate of 26.2 mgh-1 mgcat. -1, and robust durability over ten consecutive cycles, all of them are comparable to the best-reported results and exceed those of pristine Ti3C2Tx MXene. More importantly, when tested in a flow cell, the designed catalyst delivers a current density of ‒1000 mA cm-2 at a low potential of ‒1.18 V versus the reversible hydrogen electrode and maintains a high NH3 selectivity over a wide current density range. Besides, a Zn-nitrate battery with the catalyst as the cathode is assembled, which achieves a power density of 5.24 mW cm-2 and a yield rate of 1.15 mgh-1 mgcat. -1. Theoretical simulations further demonstrate that the boron dopants can optimize the adsorption and activation of NO3RR intermediates, and reduce the potential-determining step barrier, thus leading to an enhanced NH3 selectivity.

Dipole-Dipole Tuned Electronic Reconfiguration of Defective Carbon Sites for Efficient Oxygen Reduction into H2O2.

Metal-free carbon-based materials are one of the most promising electrocatalysts toward 2-electron oxygen reduction reaction (2e-ORR) for on-site production of hydrogen peroxide (H2O2), which however suffer from uncontrollable carbonizations and inferior 2e-ORR selectivity. To this end, a polydopamine (PDA)-modified carbon catalyst with a dipole-dipole enhancement is developed via a calcination-free method. The H2O2 yield rate outstandingly reaches 1.8 mol gcat -1 h-1 with high faradaic efficiency of above 95% under a wide potential range of 0.4-0.7 VRHE, overwhelming most of carbon electrocatalysts. Meanwhile, within a lab-made flow cell, the synthesized ORR electrode features an exceptional stability for over 250 h, achieved a pure H2O2 production efficacy of 306 g kWh-1. By virtue of its industrial-level capabilities, the established flow cell manages to perform a rapid pulp bleaching within 30 min. The superior performance and enhanced selectivity of 2e-ORR is experimentally revealed and attributed to the electronic reconfiguration on defective carbon sites induced by non-covalent dipole-dipole influence between PDA and carbon, thereby prohibiting the cleavage of O-O in OOH intermediates. This proposed strategy of dipole-dipole effects is universally applicable over 1D carbon nanotubes and 2D graphene, providing a practical route to design 2e-ORR catalysts.

Programmed Heterostructures for Enhanced Electrical Conductivity.

Interfacial electron transport in multicomponent systems plays a crucial role in controlling electrical conductivity. Organic-inorganic heterostructures electronic devices where all the entities are covalently bonded to each other can reduce interfacial electrical resistance, thus suitable for low-power consumption electronic operations. Programmed heterostructures of covalently bonded interfaces between ITO-ethynylbenzene (EB) and EB-zinc ferrite (ZF) nanoparticles, a programmed structure showing 67 978-fold enhancement of electrical current as compared to pristine NPs-based two terminal devices are created. An electrochemical approach is adopted to prepare nearly π-conjugated EB oligomer films of thickness ≈26 nm on ITO-electrode on which ZF NPs are chemically attached. A "flip-chip" method is employed to combine two EB-ZnFe2O4 NPs-ITO to probe electrical conductivity and charge conduction mechanism. The EB-ZnFe2O4 NPs exhibit strong electronic coupling at ITO-EB and EB-NPs with an energy barrier of 0.13 eV between the ITO Fermi level and the LUMO of EB-ZF NPs for efficient charge transport. Both the DC and AC-based electrical measurements manifest a low resistance at ITO-EB and EB-ZF NPs, revealing enhanced electrical current at ± 1.5 V. The programmed heterostructure devices can meet a strategy to create well-controlled molecular layers for electronic applications toward miniaturized components that shorten charge carrier distance, and interfacial resistance.

Electrochemical Synthesis of Urea: Co-Reduction of Nitrite and Carbon Dioxide on Binuclear Cobalt Phthalocyanine.

Exploration of molecular catalysts with the atomic-level tunability of molecular structures offers promising avenues for developing high-performance catalysts for the electrochemical co-reduction reaction of carbon dioxide (CO2) and nitrite (NO2 -) into value-added urea. In this work, a binuclear cobalt phthalocyanine (biCoPc) catalyst is prepared through chemical synthesis and applied as a C─N coupling catalyst toward urea. Achieving a remarkable Faradaic efficiency of 47.4% for urea production at -0.5 V versus reversible hydrogen electrode (RHE), this biCoPc outperforms many known molecular catalysts in this specific application. Its unique planar macromolecular structure and the increased valence state of cobalt promote the adsorption of nitrogenous and carbonaceous species, a critical factor in facilitating the multi-electron C─N coupling. Combining highly sensitive in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) with density functional theory (DFT) calculations, the linear adsorbed CO (COL) and bridge adsorbed CO (COB) is captured on biCoPc catalyst during the co-reduction reaction. COB, a pivotal intermediate in the co-reduction from CO2 and nitrite to urea, is evidenced to be labile and may be attacked by nitrite, promoting urea production. This work demonstrates the importance of designing molecular catalysts for efficient co-reduction of CO2 and nitrite to urea.

In-Plane Topological-Defect-Enriched Graphene as an Efficient Metal-Free Catalyst for pH-Universal H2O2 Electrosynthesis.

Developing efficient metal-free catalysts to directly synthesize hydrogen peroxide (H2O2) through a 2-electron (2e) oxygen reduction reaction (ORR) is crucial for substituting the traditional energy-intensive anthraquinone process. Here, in-plane topological defects enriched graphene with pentagon-S and pyrrolic-N coordination (SNC) is synthesized via the process of hydrothermal and nitridation. In SNC, pentagon-S and pyrrolic-N originating from thiourea precursor are covalently grafted onto the basal plane of the graphene framework, building unsymmetrical dumbbell-like S─C─N motifs, which effectively modulates atomic and electronic structures of graphene. The SNC catalyst delivers ultrahigh H2O2 productivity of 8.1, 7.3, and 3.9 mol gcatalyst -1 h-1 in alkaline, neutral, and acidic electrolytes, respectively, together with long-term operational stability in pH-universal electrolytes, outperforming most reported carbon catalysts. Theoretical calculations further unveil that defective S─C─N motifs efficiently optimize the binding strength to OOH* intermediate and substantially diminish the kinetic barrier for reducing O2 to H2O2, thereby promoting the intrinsic activity of 2e-ORR.

Designing Heterocyclic Covalent Organic Frameworks with Tunable Electronic Structures for Efficient Electrosynthesis of Hydrogen Peroxide.

The electrocatalytic production of hydrogen peroxide (H2O2) through the two-electron oxygen reduction reaction (2e- ORR) has garnered significant research attention in recent years due to its numerous appealing advantages, such as being eco-friendly and exhibiting high energy conversion efficiency. Metal-free carbon materials with specific catalytic sites have been recognized as potential electrocatalysts for 2e- ORR; however, the design of highly efficient catalysts with well-defined structures and long-term stability for large-scale H2O2 production remains unsatisfactory. In this study, three covalent organic frameworks (COFs) - imine-linked LZU-1, oxazole-linked LZU-190, and thiazole-linked LZU-190(S), are successfully synthesized to explore their catalytic activity in electrocatalytic H2O2 production. Among these, the carbon sites LZU-190(S) are predominantly activated by the introduced adjacent heteroatoms via electronic effects, resulting in much higher H2O2 selectivity compared to the oxazole and imine linkages. This work provides new insights into developing COFs-based electrocatalysts for efficient H2O2 generation.

Anchoring Ultrafine ß-Mo2C Clusters Inside Porous Co-NC Using MOFs for Electric-Powered Coproduction of Valuable Chemicals.

Electroredox of organics provides a promising and green approach to producing value-added chemicals. However, it remains a grand challenge to achieve high selectivity of desired products simultaneously at two electrodes, especially for non-isoelectronic transfer reactions. Here a porous heterostructure of Mo2C@Co-NC is successfully fabricated, where subnanometre ß-Mo2C clusters (<1 nm, ≈10 wt%) are confined inside porous Co, N-doped carbon using metalorganic frameworks. It is found that Co species not only promote the formation of ß-Mo2C but also can prevent it from oxidation by constructing the heterojunctions. As noted, the heterostructure achieves >96% yield and 92% Faradaic efficiency (FE) for aldehydes in anodic alcohol oxidation, as well as >99.9% yield and 96% FE for amines in cathodal nitrocompounds reduction in 1.0 M KOH. Precise control of the reaction kinetics of two half-reactions by the electronic interaction between ß-Mo2C and Co is a crucial adjective. Density functional theory (DFT) gives in-depth mechanistic insight into the high aldehyde selectivity. The work guides authors to reveal the electrooxidation nature of Mo2C at a subnanometer level. It is anticipated that the strategy will provide new insights into the design of highly effective bifunctional electrocatalysts for the coproduction of more complex fine chemicals.

Artificial and Biosynthetic Nanoparticles Boost Bioelectrochemical Reactions via Efficient Bidirectional Electron Transfer of Shewanella loihica.

Bioelectrochemical reactions using whole-cell biocatalysts are promising carbon-neutral approaches because of their easy operation, low cost, and sustainability. Bidirectional (outward or inward) electron transfer via exoelectrogens plays the main role in driving bioelectrochemical reactions. However, the low electron transfer efficiency seriously inhibits bioelectrochemical reaction kinetics. Here, a three dimensional and artificial nanoparticles-constituent inverse opal-indium tin oxide (IO-ITO) electrode is fabricated and employed to connect with exoelectrogens (Shewanella loihica PV-4). The above electrode collected 128-fold higher cell density and exhibited a maximum current output approaching 1.5 mA cm-2 within 24 h at anode mode. By changing the IO-ITO electrode to cathode mode, the exoelectrogens exhibited the attractive ability of extracellular electron uptake to reduce fumarate and 16 times higher reverse current than the commercial carbon electrode. Notably, Fe-containing oxide nanoparticles are biologically synthesized at both sides of the outer cell membrane and probably contributed to direct electron transfer with the transmembrane c-type cytochromes. Owing to the efficient electron exchange via artificial and biosynthetic nanoparticles, bioelectrochemical CO2 reduction is also realized at the cathode. This work not only explored the possibility of augmenting bidirectional electron transfer but also provided a new strategy to boost bioelectrochemical reactions by introducing biohybrid nanoparticles.

Electrochemical Nitrate-to-Ammonia Conversion Enabled by Carbon-Decoration of Ni─GaOOH Synthesized via Plasma-Assisted CO2 Reduction.

The release of nitrates into the environment leads to contaminated soil and water that poses a health risk to humans and animals. Due to the transition to renewable energy-based technologies, an electrochemical approach is an emerging option that can selectively produce valuable ammonia from nitrate sources. However, traditional metal-based electrocatalysts often suffer from low nitrate adsorption that reduces NH3  production rates. Here, a Ni-GaOOH-C/Ga electrocatalyst for electrochemical nitrate conversion into NH3 is synthesized via a low energy atmospheric-pressure plasma process that reduces CO2  into highly dispersed activated carbon on dispersed Ni─GaOOH particles produced from a liquid metal Ga─Ni alloy precursor. Nitrate conversion rates of up to 26.3 µg h-1  mg-1 cat  are achieved with good stability of up to 20 h. Critically, the presence of carbon centers is central to improved performance where both Ni─C and NiO─C interfaces act as NO3-  adsorption and reduction centers during the reaction. Density functional theory (DFT) calculations indicate that the NiO─C and Ni─C reaction sites reduce the Gibbs free energy required for NO3-  reduction to NH3  compared to NiO and Ni. Importantly, catalysts without carbon centers do not produce NH3 , emphasizing the unique effects of incorporating carbon nanoparticles into the electrocatalyst.

Boosting Up Electrosynthesis of Urea with Nitrate and Carbon Dioxide via Synergistic Effect of Metallic Iron Cluster and Single-Atom.

Electrocatalytic conversion of nitrates and carbon dioxide to urea under ambient conditions shows promise as a potential substitute for traditional urea synthesis processes characterized by high consumption and pollution. In this study, a straightforward one-pot method is employed to prepare a highly efficient FeNC-Fe1N4 electrocatalyst, consisting of atomically dispersed Fe1N4 sites and metallic Fe clusters (FeNC) with particle size of 4-7 nm. The FeNC-Fe1N4 catalyst exhibits remarkable electrocatalytic activity for urea synthesis from nitrate anion (NO3 -) and carbon dioxide (CO2), achieving a urea production rate of 38.2 mmol gcat -1 h-1 at -0.9 V (vs RHE) and a Faradaic efficiency of 66.5% at -0.6 V (vs RHE). Both experimental and theoretical results conclusively demonstrate that metallic Fe clusters and Fe1N4 species provide active sites for the adsorption and activation of NO3 - and CO2, respectively, and the synergistic effect between Fe1N4 and metallic Fe clusters significantly enhances the electrochemical efficiency of urea synthesis. In all, this work contributes to the rational design and comprehensive synthesis of a dual-active site iron-based electrocatalyst, facilitating efficient and sustainable urea synthesis.

Single-Atom Co─O4 Sites Embedded in a Defective-Rich Porous Carbon Layer for Efficient H2O2 Electrosynthesis.

The production of hydrogen peroxide (H2O2) via the two-electron electrochemical oxygen reduction reaction (2e- ORR) is an essential alteration in the current anthraquinone-based method. Herein, a single-atom Co─O4 electrocatalyst is embedded in a defective and porous graphene-like carbon layer (Co─O4@PC). The Co─O4@PC electrocatalyst shows promising potential in H2O2 electrosynthesis via 2e- ORR, providing a high H2O2 selectivity of 98.8% at 0.6 V and a low onset potential of 0.73 V for generating H2O2. In situ surface-sensitive attenuated total reflection Fourier transform infrared spectra and density functional theory calculations reveal that the electronic and geometric modification of Co─O4 induced by defective carbon sites result in decreased d-band center of Co atoms, providing the optimum adsorption energies of OOH* intermediate. The H-cell and flow cell assembled using Co─O4@PC as the cathode present long-term stability and high efficiency for H2O2 production. Particularly, a high H2O2 production rate of 0.25 mol g-1 cat h-1 at 0.6 V can be obtained by the flow cell. The in situ-generated H2O2 can promote the degradation of rhodamine B and sterilize Staphylococcus aureus via the Fenton process. This work can pave the way for the efficient production of H2O2 by using Co─O4 single atom electrocatalyst and unveil the electrocatalytic mechanism.

The electron transport chain of Shewanella oneidensis MR-1 can operate bidirectionally to enable microbial electrosynthesis.

Extracellular electron transfer is a process by which bacterial cells can exchange electrons with a redox-active material located outside of the cell. In Shewanella oneidensis, this process is natively used to facilitate respiration using extracellular electron acceptors such as Fe(III) or an anode. Previously, it was demonstrated that this process can be used to drive the microbial electrosynthesis (MES) of 2,3-butanediol (2,3-BDO) in S. oneidensis exogenously expressing butanediol dehydrogenase (BDH). Electrons taken into the cell from a cathode are used to generate NADH, which in turn is used to reduce acetoin to 2,3-BDO via BDH. However, generating NADH via electron uptake from a cathode is energetically unfavorable, so NADH dehydrogenases couple the reaction to proton motive force. We therefore need to maintain the proton gradient across the membrane to sustain NADH production. This work explores accomplishing this task by bidirectional electron transfer, where electrons provided by the cathode go to both NADH formation and oxygen (O2) reduction by oxidases. We show that oxidases use trace dissolved oxygen in a microaerobic bioelectrical chemical system (BES), and the translocation of protons across the membrane during O2 reduction supports 2,3-BDO generation. Interestingly, this process is inhibited by high levels of dissolved oxygen in this system. In an aerated BES, O2 molecules react with the strong reductant (cathode) to form reactive oxygen species, resulting in cell death.IMPORTANCEMicrobial electrosynthesis (MES) is increasingly employed for the generation of specialty chemicals, such as biofuels, bioplastics, and cancer therapeutics. For these systems to be viable for industrial scale-up, it is important to understand the energetic requirements of the bacteria to mitigate unnecessary costs. This work demonstrates sustained production of an industrially relevant chemical driven by a cathode. Additionally, it optimizes a previously published system by removing any requirement for phototrophic energy, thereby removing the additional cost of providing a light source. We also demonstrate the severe impact of oxygen intrusion into bioelectrochemical systems, offering insight to future researchers aiming to work in an anaerobic environment. These studies provide insight into both the thermodynamics of electrosynthesis and the importance of the bioelectrochemical systems' design.

Metabolic engineering strategies to enable microbial electrosynthesis utilization of CO2: recent progress and challenges.

Microbial electrosynthesis (MES) is a promising technology that mainly utilizes microbial cells to convert CO2 into value-added chemicals using electrons provided by the cathode. However, the low electron transfer rate is a solid bottleneck hindering the further application of MES. Thus, as an effective strategy, genetic tools play a key role in MES for enhancing the electron transfer rate and diversity of production. We describe a set of genetic strategies based on fundamental characteristics and current successes and discuss their functional mechanisms in driving microbial electrocatalytic reactions to fully comprehend the roles and uses of genetic tools in MES. This paper also analyzes the process of nanomaterial application in extracellular electron transfer (EET). It provides a technique that combines nanomaterials and genetic tools to increase MES efficiency, because nanoparticles have a role in the production of functional genes in EET although genetic tools can subvert MES, it still has issues with difficult transformation and low expression levels. Genetic tools remain one of the most promising future strategies for advancing the MES process despite these challenges.

Electrochemical Synthesis of Itaconic Acid Derivatives via Chemodivergent Single and Double Carboxylation of Allenes with CO2.

Leveraging electrochemistry, a new synthesis of non-natural derivatives of itaconic acid is proposed by utilizing carbon dioxide (CO2) as a valuable C1 synthon. An electrochemical cross-electrophile coupling between allenoates and CO2 was targeted, allowing for the synthesis of both mono- and di-carboxylation products in a catalyst- and additive-free environment (yields up to 87%, 30 examples). Elaboration of the model mono-carboxylation product, and detailed cyclovoltammetric, as well as mechanistic analyses complete the present investigation.

Nickel-Catalyzed Intramolecular Hydrosilylation of Alkynes: Embracing Conventional and Electrochemical Routes.

Nickel-catalyzed intramolecular hydrosilylation can be efficiently achieved with high regio- and stereoselectivities through two distinct methodologies. The first approach utilizes a conventional method, involving the reduction of nickel salt (NiBr2-2,2'-bipyridine) using manganese metal. The second method employs a one-step electrochemical reaction, utilizing the sacrificial anode process and NiBr2bipy catalysis. Both methods yield silylated heterocycles in good to high yields through a syn-exo-dig cyclization process. Control experiments and molecular electrochemistry (cyclic voltammetry) provided further insights into the reaction mechanism.