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.

A relay catalysis strategy for enantioselective nickel-catalyzed migratory hydroarylation forming chiral α-aryl alkylboronates

Selective conversion of methanol to aromatics with superior catalytic stability by relay catalysis over quadruple ZSM-5 sequence beds with gradient-increasing acidity

Involving eight electron transfer process and multiple intermediates of nitrate reduction reaction (NO3 RR) leads to a sluggish kinetic and low Faradic efficiency, therefore, it's essential to get an insight into the reaction mechanism to develop highly efficient electrocatalyst. Herein, a series of reduced graphene oxide supported RuCu alloy catalysts (Rux Cuy /rGO) were fabricated and used for the direct reduction of NO3 - to NH3 . It is found that the Ru1 Cu10 /rGO shows the ammonia formation rate of 0.38mmol cm-2 h-1 (loading 1mg/cm2 ) and the ammonia Faradic efficiency (FE) of 98% under an ultralow potential of -0.05V versus RHE, which is comparable to Ru catalyst. The highly efficient activity of Ru1 Cu10 /rGO can be attributed to the synergetic effect between Ru and Cu sites via a relay catalysis, in which the Cu shows the exclusively efficient activity for the reduction of NO3 - to NO2 - and Ru exhibits the superior activity for NO2 - to NH3 . In addition, the doping of Ru into Cu tunes the d-band center of alloy and effectively modulates the adsorption energy of the NO3 - and NO2 - , which promotes the direct reduction of NO3 - to NH3 . This synergetic electrocatalysis strategy opens a new avenue for developing highly efficient multifunctional catalysts. This article is protected by copyright. All rights reserved.

This work describes the first example of using chiral catalysts to control site-selectivity for the glycosylations of complex polyols such as 6-deoxyerythronolide B and oleandomycin-derived macrolactones. The regiodivergent introduction of sugars at the C3, C5, and C11 positions of macrolactones was achieved by selecting appropriate chiral acids as catalysts or through introduction of stoichiometric boronic acid-based additives. BINOL-based chiral phosphoric acids (CPAs) were used to catalyze highly selective glycosylations at the C5 positions of macrolactones (up to 99:1 rr), whereas the use of SPINOL-based CPAs resulted in selectivity switch and glycosylation of the C3 alcohol (up to 91:9 rr). Additionally, the C11 position of macrolactones was selectively functionalized through traceless protection of the C3/C5 diol with boronic acids prior to glycosylation. Investigation of the reaction mechanism for the CPA-controlled glycosylations revealed the involvement of covalently linked anomeric phosphates rather than oxocarbenium ion pairs as the reactive intermediates.

Relay catalysis over Pd-catalysts induced by two divergent ligands for cascade bis-alkoxycarbonylation of alkynes

Achieving precise regioselectivity in the hydroamination of alkenes is in high demand yet remains a longstanding challenge, particularly when electronically competing β-substituents are present. Here, we report a dual boron/iron catalytic system that enables the unprecedented hydroamidation of α,β-unsaturated esters to exclusively access α-amidated esters under mild conditions. The strategy harnesses the Lewis acidity of B(C6F5)3 to rapidly generate reactive silyl ketene acetal intermediates, which are subsequently intercepted by in situ generated iron nitrenoids. Central to this cooperative activation mode is the dual role of the chloride anion in modulating both boron and iron catalytic reactivity. This protocol is operationally simple, requiring no tailored ligands, light, or electrochemical setup, and proceeds efficiently with only 1 mol % of boron and iron catalysts. The system exhibits a broad scope of unsaturated esters, tolerating β-aryl, -alkyl, -silyl, -perfluoroalkyl, and -boryl groups. This work lays the foundation for universal α-selective hydrofunctionalization strategies across electronically complex substrates.

A novel relay catalytic strategy for the asymmetric functionalization of terminal alkynes by synergistically integrating Rh-catalyzed hydroformylation with N-heterocyclic carbene (NHC)-catalyzed asymmetric annulation has been developed. This dual-catalysis platform overrides the innate reactivity of alkynes, enabling direct and efficient access to polysubstituted chiral cyclopentenes from simple terminal alkynes, enones, and syngas. The transformation proceeds smoothly under mild conditions, delivering a broad range of chiral cyclopentenes in good yields, with high diastereoselectivities and excellent enantioselectivities (up to 16:1 dr, up to 99% ee).

Electrocatalytic dehydrogenative C(sp3)–H/C(sp)–H cross-coupling of tetrahydroisoquinolines with terminal alkynes has been achieved in a continuous-flow microreactor through 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)/copper relay catalysis. The reaction is easily scalable and requires low concentration of supporting electrolyte and no external chemical oxidants or ligands, providing straightforward and sustainable access to 2-functionalized tetrahydroisoquinolines.

Catenated cages are generally considered thermodynamically more stable than their constituent monomeric cages. However, the catenation mechanism is yet to be elucidated; it would require systematic...

Tuberculosis remains today one of the top three fatal infectious diseases, together with acquired immune deficiency syndrome (AIDS) and malaria. During the last decade, 90 million new infections occurred, resulting in approximately 30 million deaths. Although there is currently effective chemotherapy, consisting of three specific drugs, this regimen must be continued for a period of at least 6 months, which in many cases, results in problems with compliance. Lack of compliance further impacts on the development of multidrug-resistant strains of the bacterium, which consequently raises the cost of treatment, making the expense of curing tuberculosis prohibitive in many developing countries. Despite the enormous numbers of people infected with this organism, it is estimated that only 10% of affected individuals show evidence of clinical symptoms. Many parameters, notably socio-economic factors, co-infection with human immunodeficiency virus (HIV) and genetic predisposition of the host, influence the susceptibility to disease. Much work has been invested to elucidate the biology of the interaction between Mycobacterium tuberculosis and its host, both in experimental animal models and in clinical studies. Here we review some of the latest developments in the understanding of the immune response required to control this pathogen. It is hoped that further progress in this field will lead to a more rational approach towards the development of an effective vaccine and novel chemotherapeutic agents.

CpRu-catalyzed asymmetric allylic alkylation serves as a versatile synthetic tool but remains underexplored. Herein, we report a relay system combining achiral Rh2(OAc)4 and a chiral pyridine-oxazoline-ligated Cp*Ru catalyst for asymmetric coupling of cinnamyl chlorides with diazo esters, generating silyl enol ethers in situ as key nucleophilic intermediates. This strategy affords chiral tetrahydrofuran derivatives with two vicinal stereocenters. Catalyst compatibility, excellent regioselectivity, and good enantioselectivity highlight its potential. Computational studies reveal the crucial role of Ru-centered chirality in reaction control.

A closely packed hybrid electrocatalyst Pt1.5Ni1−x/Ni–N–C was engineered by a gas-promoted dealloying process, ensuring the relay catalysis of the reaction intermediates at Pt alloy and Ni single sites, thus achieving high performance in PEMFCs.

Atomically dispersed catalysts have opened new frontiers in electrocatalysis by maximizing metal atom utilization and enabling precisely defined active sites with dual‐atom catalysts (DACs) standing out for their distinctive capacity to facilitate complex multi‐electron, multi‐step transformations, such as the electrocatalytic CO 2 reduction reaction (CO 2 RR). The cooperative interplay between two adjacent metal centers in DACs orchestrates a symphonic interaction, conferring dynamic roles in activating reactants, stabilizing reaction intermediates, and steering reaction pathways, thereby enhancing both catalytic activity and product selectivity. This review presents a focused investigation of DAC‐mediated CO 2 RR, categorizing their mechanistic functions into five representative paradigms: electronic promotion, synergistic bifunctionality, relay catalysis, intermediate coupling, and selective competition. By elucidating these mechanisms with illustrative examples, we establish clear structure–activity–selectivity correlations and underscore the unique catalytic versatility afforded by dual‐site interactions. We also highlight critical challenges and emerging opportunities in DAC development, spanning precision synthesis, advanced characterization, mechanistic elucidation, and practical deployment, with the aim of inspiring the rational advancement of future CO 2 RR catalysts.

Copper-Catalyzed Highly Enantioselective 1,4-Protoboration of Terminal 1,3-Dienes