Constructing molecule-metal relay catalysis over heterophase metallene for high-performance rechargeable zinc-nitrate/ethanol batteries.

Zinc-nitrate batteries can integrate energy supply, ammonia electrosynthesis, and sewage disposal into one electrochemical device. However, current zinc-nitrate batteries still severely suffer from the limited energy density and poor rechargeability. Here, we report the synthesis of tetraphenylporphyrin (tpp)-modified heterophase (amorphous/crystalline) rhodium-copper alloy metallenes (RhCu M-tpp). Using RhCu M-tpp as a bifunctional catalyst for nitrate reduction reaction (NO3RR) and ethanol oxidation reaction in neutral solution, a highly rechargeable and low-overpotential zinc-nitrate/ethanol battery is successfully constructed, which exhibits outstanding energy density of 117364.6 Wh kg-1cat, superior rate capability, excellent cycling stability of ~400 cycles, and potential ammonium acetate production. Ex/in situ experimental studies and theoretical calculations reveal that there is a molecule-metal relay catalysis in NO3RR over RhCu M-tpp that significantly facilitates the ammonia selectivity and reaction kinetics via a low energy barrier pathway. This work provides an effective design strategy of multifunctional metal-based catalysts toward the high-performance zinc-based hybrid energy systems.

Reversible Hydrogen Acceptor-Donor Enables Relay Mechanism for Nitrate-to-Ammonia Electrocatalysis.

Electrocatalytic nitrate reduction is a crucial process for sustainable ammonia production. However, to maximize ammonia yield efficiency, this technology inevitably operates at the potentials more negative than 0 V vs. RHE, leading to high energy consumption and competitive hydrogen evolution. To eradicate this issue, hydrogen tungsten bronze (HxWO3) as reversible hydrogen donor-acceptor is partnered with copper (Cu) to enable a relay mechanism at potentials positive than 0 V vs. RHE, which involves rapid intercalation of H into HxWO3 lattice, prompt de-intercalation of the lattice H and transfer onto Cu, and spontaneous H-mediated nitrate-to-ammonia conversion on Cu. The resulting catalysts demonstrated a high ammonia yield rate of 3332.9±34.1 mmol gcat-1 h-1 and a Faraday efficiency of ~100 % at 0.10 V vs. RHE, displaying a record-low estimated energy consumption of 17.6 kWh kgammonia-1. Using these catalysts, we achieve continuous ammonia production in an enlarged flow cell at a real energy consumption of 17.0 kWh kgammonia-1.

Value-Added Upcycling of PET to 1,4-Cyclohexanedimethanol by a Hydrogenation/Hydrogenolysis Relay Catalysis.

We present an innovative process for directly transforming poly(ethylene terephthalate) (PET), a polymer extensively used in food and beverage packaging, into trans-isomer-enriched 1,4-cyclohexanedimethanol (CHDM), a key ingredient in advanced specialty polymers. Our approach leverages a dual-catalyst system featuring palladium on reduced graphene oxide (Pd/r-GO) and oxalate-gel-derived copper-zinc oxide (og-CuZn), utilizing hydrogenation/hydrogenolysis relay catalysis. This method efficiently transforms PET into polyethylene-1,4-cyclohexanedicarboxylate (PECHD), which is then converted into CHDM with an impressive overall yield of 95 % in a two-stage process. Our process effectively handles various post-consumer PET plastics, converting them into CHDM with yields between 78 % and 89 % across different substrates. Additionally, we demonstrate the applicability and scalability of this approach through a temperature-programmed three-stage relay process on a 10-gram scale, which results in purified CHDM with an isolated yield of 87 % and a notably higher trans/cis ratio of up to 4.09/1, far exceeding that of commercially available CHDM. This research not only provides a viable route for repurposing PET waste but also enhances the control of selectivity patterns in multistage relay catalysis.

Triple Regulations via Fe Redox Boosting Nitrate Reduction to Ammonia at Industrial Current Densities.

Electrochemical nitrate reduction reaction (NO3 -RR) has promising prospects for green synthesis of ammonia and environmental remediation. However, the performance of catalysts at high current density usually suffers from the high energy barrier for the nitrate (NO3 -) to nitrite (NO2 -) and the competitive hydrogen evolution. Herein, we proposed a two-step relay mechanism through spontaneous redox reaction followed electrochemical reaction by introducing low-valence Fe species into Ni2P nanosheets to significantly enhance the NO3 -RR performance at industrial current density. The existence of low-valence Fe species bypasses the NO3 - to NO2 - step through the spontaneous redox with NO3 - to produce NO2 - and Fe2O3, regulates the electronic structure of Ni2P to reduce the barrier of NO2 - to NH3, thirdly prohibits the hydrogen evolution by consuming the excess active hydrogen through reduction of Fe2O3 to recover low-valence Fe species. The triple regulations via Fe redox during the two-step relay reactions guarantee the Fe-Ni2P@NF high ammonia yield of 120.1 mg h-1 cm-2 with Faraday efficiency of more than 90% over a wide potential window and a long-term stability of more than 130 h at ~1000 mA cm-2. This work provides a new strategy to realize the design and synthesis of nitrate reduction electrocatalysts at high current densities.

Copper/Ruthenium Relay Catalysis for Stereodivergent Access to δ-Hydroxy α-Amino Acids and Small Peptides.

An atom- and step-economical and redox-neutral cascade reaction enabled by asymmetric bimetallic relay catalysis by merging a ruthenium-catalyzed asymmetric borrowing-hydrogen reaction with copper-catalyzed asymmetric Michael addition has been realized. A variety of highly functionalized 2-amino-5-hydroxyvaleric acid esters or peptides bearing 1,4-non-adjacent stereogenic centers have been prepared in high yields with excellent enantio- and diastereoselectivity. Judicious selection and rational modification of the Ru catalysts with careful tuning of the reaction conditions played a pivotal role in stereoselectivity control as well as attenuating undesired α-epimerization, thus enabling a full complement of all four stereoisomers that were otherwise inaccessible in previous work. Concise asymmetric stereodivergent synthesis of the key intermediates for biologically important chiral molecules further showcases the synthetic utility of this methodology.

Interfacial Thermoconvection and Atomic Relay Catalysis Enable Equilibrium Shifting and Rapid Glucose-to-Fructose Isomerization.

The aqueous glucose-to-fructose isomerization is controlled by thermodynamics to an equilibrium limit of ~50% fructose yield. However, here we report an in-situ fructose removal strategy enabled by an interfacial local photothermal effect in combination with relay catalysis of geminal and isolated potassium single atoms (K SAs) on graphene-type carbon (Ksg/GT) to effectively bypass the equilibrium limit and markedly speed up glucose-to-fructose isomerization. At 25 ºC, an unprecedented fructose yield of 68.2% was obtained over Ksg/GT in an aqueous solution without any additives under 30-min solar-like irradiation. Mechanistic studies expounded that the interfacial thermoconvection caused by the local photothermal effect of the graphene-type carbon and preferable glucose adsorption on single-atom K could facilitate the release of in-situ formed fructose. The geminal K SAs were prone to form a stable metal-glucose complex via bidentate coordination, and could significantly reduce the C-H bond electron density by light-driven electron transfer toward K. This facilitated the hydride shift rate-determining step and expedited glucose isomerization. In addition, isolated K SAs favored the subsequent protonation and ring-closure process to furnish fructose. The integration of the interfacial thermoconvection-enhanced in-situ removal protocol and tailored atomic catalysis opens a prospective avenue for boosting equilibrium-limited reactions under mild conditions.

A Merger of Relay Catalysis with Dynamic Kinetic Resolution Enables Enantioselective ß-C(sp3)-H Arylation of Alcohols.

The conceptual merger of relay catalysis with dynamic kinetic resolution strategy is reported to enable regio- and enantioselective C(sp3)-H bond arylation of aliphatic alcohols, forming enantioenriched ß-aryl alcohols typically with >90 : 10 enantiomeric ratios (up to 98 : 2 er) and 36-74 % yields. The starting materials bearing neighbouring stereogenic centres can be converted to either diastereomer of the ß-aryl alcohol products, with >85 : 15 diastereomeric ratios determined by the catalysts. The reactions occur under mild conditions, ensuring broad compatibility, and involve readily available aryl bromides, an inorganic base, and commercial Ru- and Pd-complexes. Mechanistic experiments support the envisioned mechanism of the transformation occurring through a network of regio- and stereoselective processes operated by a coherent Ru/Pd-dual catalytic system.

Efficient Synthesis of Diaryl Quaternary Centers by Rh(II)/Xantphos Catalyzed Relay C-H Functionalization and Allylic Alkylation.

A three-component reaction of N, N-disubstituted aniline, α-diazo ester, and an allylic electrophile has been realized by [Rh(II)]2 /Xantphos catalysis, providing a direct access to various aniline derivatives bearing diaryl allylic quaternary centers in good yields. The synthetic utility of this protocol was demonstrated by facile derivatization of the products for preparation of biologically relevant molecules and structural scaffolds, which offers a high potential for increasing the molecular diversity. Mechanistic studies identified α, α-diarylacetate species as an active intermediate, thereby revealing the presence of a C(sp2 )-H functionalization of aniline derivatives/allylic alkylation cascade in this attractive catalytic transformation.

Enantioselective C-H Bond Functionalization Involving Arene Ruthenium(II) Catalysis.

The p-Cymene ruthenium(II) complex is one of the most widely used catalysts in C-H activation. However, enantioselective C-H activation promoted by arene ruthenium(II) complexes has not been realized until recently. The revealed strategies include intramolecular nitrene C-H insertion, the use of chiral transient directing groups, chiral carboxylic acid, relay catalysis, and chiral arene ligands. In this minireview, these advances are summarized and discussed in the hope of spurring further developments.

Utilizing Nitroarenes and HCHO to Directly Construct Functional N-Heterocycles by Supported Cobalt/Amino Acid Relay Catalysis.

Due to the generation of multiple intermediates during the nitroarene reduction, precise interception of single one to develop tandem reactions involving both C-C and C-N bond formations still remains a significant challenge. Herein, the relay catalysis of a supported bifunctional cobalt catalyst with l-proline has been successfully applied to establish a bran-new reductive annulation reaction of nitroarenes and formaldehyde, which enables direct and diverse construction of both symmetrical and unsymmetrical 1,3-diaryl imidazolines. It proceeds with operational simplicity, good substrate and functionality compatibility, and excellent step and atom-efficiency. Mechanistic studies reveal that the Co-catalyst exhibits a synergistic effect on the formation of key N-hydroxy imine, and the l-proline subsequently facilitates the key C-C bond formation. The current work opens a door to develop useful transformations with nitroarenes by reduction-interrupted strategy.

Photocatalytic sequential C-H functionalization expediting acetoxymalonylation of imidazo heterocycles.

The importance of functionalized imidazo heterocycles has often been featured in several impactful research both from academia and industry. Herein, we report a direct C-3 acetoxymalonylation of imidazo heterocycles using relay C-H functionalization enabled by organophotocatalysis starring zinc acetate in the triple role of an activator, ion scavenger as well as an acetylating reagent. The mechanistic investigation revealed a sequential sp2 and sp3 C-H activation, followed by functionalization driven by zinc acetate coupled with the photocatalyst PTH. A variety of imidazo[1,2-a]pyridines and related heterocycles were explored as substrates along with several active methylene reagents, all generating the products with excellent yields and regioselectivity, thus confirming excellent functional group tolerability.

Enantioselective Cascade Annulation of α-Amino-ynones and Enals Enabled by Gold and Oxidative NHC Relay Catalysis.

We report herein an unprecedented gold and oxidative NHC relay catalysis that enables highly enantioselective cascade annulation between readily available α-amino-ynones with enals. This method utilizes the in situ-generated pyrrolin-4-ones as a novel and versatile synthon, which engage with α,ß-unsaturated acylazolium intermediates generated from enals by oxidative NHC catalysis to produce pyrrole-fused lactones in high yield and excellent enantioselectivity. Synthetic utility of the lactone products is also demonstrated by facile conversion to densely functionalized pyrroles and pyrrolin-4-ones in high yields with excellent stereopurity.

Modular and Fast Synthesis of Versatile Secondary α,α-Dialkyl Boronates via Deoxygenative Alkylboration of Aldehydes.

Secondary α,α-dialkyl boronates are widely used due to their great versatility. Herein we report an unprecedented deoxygenative alkylboration of aldehydes, a facile method to access this type of products. A sequence of difunctionalization can be obtained smoothly from the readily available aldehydes in only two steps. This difunctionalization of aldehydes rather than conventional alkenes also opens new possibilities within the field.

Asymmetric Double Hydroxycarbonylation of Alkynes to Chiral Succinic Acids Enabled by Palladium Relay Catalysis.

A Pd-catalyzed asymmetric double hydroxycarbonylation of terminal alkynes was developed by using relay catalysis, providing a highly efficient route to chiral succinic acids (41 examples, 76-94 %, 94-99 % ee). Key to success was the combinatorial use of a Pd precursor with two distinct phosphine ligands in one pot. The synthetic utilities of this protocol were showcased in the facile synthesis of key intermediates for chiral pharmaceuticals.

Stereodivergent Construction of 1,4-Nonadjacent Stereocenters via Hydroalkylation of Racemic Allylic Alcohols Enabled by Copper/Ruthenium Relay Catalysis.

An unprecedented hydroalkylation of racemic allylic alcohols and racemic ketimine esters enabled by Cu/Ru relay catalysis has been developed via merging the ruthenium-catalyzed asymmetric borrowing-hydrogen reaction with a copper-catalyzed asymmetric Michael addition in a one-pot procedure. The current method enables the efficient preparation of highly functionalized δ-hydroxyesters bearing 1,4-nonadjacent stereocenters in good yields with high levels of diastereoselectivity and excellent enantioselectivity under mild reaction conditions. The full complement of the four stereoisomers of hydroalkylation products could be readily accessed by orthogonal permutations of two chiral metal catalysts. The current work highlights the power of relay catalysis for the stereodivergent construction of 1,4-nonadjacent stereocenters that were otherwise inaccessible.

Tandem Catalytic Indolization/Enantioconvergent Substitution of Alcohols by Borrowing Hydrogen to Access Tricyclic Indoles.

An efficient tandem catalysis method is achieved for the direct conversion of alcohol-containing alkynyl anilines to valuable chiral 2,3-fused tricyclic indoles. This method relies on a tandem indolization followed by enantioconvergent substitution of alcohols via borrowing hydrogen to construct two rings in one step, enabled by relay and cooperative catalysis of a chiral iridium complex with a chiral phosphoric acid. Highly diastereoselective transformations of the tricyclic indole products also provide efficient access to a diverse array of complex polycyclic indoline compounds.

Asymmetric Deoxygenative Alkynylation of Tertiary Amides Enabled by Iridium/Copper Bimetallic Relay Catalysis.

A variety of inert tertiary amides have been successfully transformed into synthetically important chiral propargylamines in high yields with good to excellent enantioselectivities via a relayed sequence of Ir catalyzed partial reduction and Cu/GARPHOS catalyzed asymmetric alkynylation with terminal alkynes. The reaction was readily extended to some drug molecules and the transformations of representative products have been demonstrated, thus attesting the practical utilities and the robust nature of the protocol.

Gold and Carbene Relay Catalytic Enantioselective Cycloisomerization/Cyclization Reactions of Ynamides and Enals.

The combined use of gold as transition metal catalyst and N-heterocyclic carbene (NHC) as organic catalyst in the same solution for relay catalytic reactions was disclosed. The ynamide substrate was activated by gold catalyst to form unsaturated ketimine intermediate that subsequently reacted with the enals (via azolium enolate intermediate generated with NHC) effectively to form bicyclic lactam products with excellent diastereo- and enantio-selectivities. The gold and NHC coordination and dissociation can be dynamic and tunable events, and thus allow the co-existence of both active metal and carbene organic catalysts in appreciable concentrations, for the dual catalytic reaction to proceed.

Stereoconvergent, Redox-Neutral Access to Tetrahydroquinoxalines through Relay Epoxide Opening/Amination of Alcohols.

We present an economical catalytic procedure to convert readily available 1,2-diaminobenzenes and terminal epoxides into valuable 1,2,3,4-tetrahydroquinoxalines in a highly enantioselective fashion. This procedure operates through relay zinc and iridium catalysis, and achieves redox-neutral and stereoconvergent production of valuable chiral heterocycles from racemic starting materials with water as the only side product. The use of commercially available reagents and catalysts and a convenient procedure also make this catalytic method attractive for practical application.

Catalytic Generation of C1 Ammonium Enolates from Halides and CO for Asymmetric Cascade Reactions.

A general strategy for the design of asymmetric cascade reactions using readily available halides and carbon monoxide (CO) as substrates is developed. The key is the catalytic generation of C1-ammonium enolates for the subsequent asymmetric cascade reactions through the combination of palladium-catalyzed carbonylation and chiral Lewis base catalysis. Utilizing this strategy, we have established asymmetric formal [1+1+4] and [1+1+2] reactions to afford chiral dihydropyridones and ß-lactams with high yields and high enantio- and diastereoselectivities.