Finn Moeller

In this work, we report a novel light-mediated desaturation strategy enabled by electron donor–acceptor complex formation. DFT and mechanistic studies reveal that the reaction proceeds via single-electron transfer, hydrogen atom transfer, and base-mediated deprotonation sequentially with pyridinium salt serving dually as oxidant and base, and hexafluoroisopropanol functioning as solvent and radical mediator. Notably, this strategy demonstrates broad substrate scope, enabling efficient synthesis of quinolinones, coumarins, and flavones, and also facilitates the late-stage functionalization of drug molecules.

Abstract

Recently, electron donor–acceptor (EDA) complex-mediated organic synthetic strategies have emerged as powerful tools for diverse bond-forming transformations; however, their efficiency often diminishes when ionic reactants are involved. This limitation arises from the requirement of polar solvents such as DMSO or DMF to solubilize ionic species for the formation of effective EDA complex. Consequently, these solvents engage in competing EDA complex formation or disrupt ionization equilibria. In parallel, there is a pressing necessity of modern and efficient strategy to achieve dehydrogenation reactions, which are in general limited by the drawbacks of traditional approaches. To address both, herein, we disclose an innovative desaturation strategy based on the formation of an EDA complex between a dihydrogenated organic substrate and an N-methoxy pyridinium salt. In our study, solubility issues, which are associated with the pyridinium salt, are effectively addressed by using hexafluoroisopropanol (HFIP). Beyond enhancing solubility, HFIP also functions as a transient H-shuttle, significantly reducing the activation energy for this transformation. This cooperative interplay between HFIP and the pyridinium salt enables the efficient and selective desaturation of a broad range of heterocyclic carbonyl compounds—including quinolinones, coumarins, and flavones—which are valuable scaffolds in pharmaceutical and agrochemical research. At the end, detailed mechanistic studies with the aid of experiments as well as DFT studies clearly disclose the mechanism as well as the important role of HFIP in this reaction.

Nature Communications, Published online: 27 October 2025; doi:10.1038/s41467-025-65413-8

Retraction Note: Vasculogenic mimicry formation in EBV-associated epithelial malignancies

Recently, Chi, Huang, Qu et al. reported a new cathode for Zn–I₂ batteries based on the 2I₃ ⁻@BMT anion complex. In this correspondence, we highlight the lack of proper authorship attribution for the BMT ligand and its complexes with the triiodide anion (I₃ ⁻). We also highlight major issues in the material's characterization and theoretical calculations, as well as inconsistencies in the equilibrium data for I₃ ⁻ binding by BMT in solution.

Abstract

In a recent research article (doi.org/10.1002/anie.202507497), Chi, Huang, Qu et al. described a multifunctional cathode for Zn–I₂ batteries based on a s-tetrazine ligand bearing two morpholine pendants, forming the active 2I₃ ⁻@BMT complex. In addition to the lack of proper attribution for prior reports by other authors (doi.org/10.1021/acs.inorgchem.6b01138; doi.org/10.1039/c7dt00134g) regarding the design of this ligand as an anion receptor, its synthesis and its ability to form triiodide complexes, the article is affected by serious scientific/technical flaws. The actual composition of the 2I₃ ⁻@BMT complex was not established, and protonation of morpholine groups in aqueous media, essential to the formation of the triiodide complex, was overlooked, despite prior studies and crystallographic evidence. The 2:1 I₃ ⁻:BMT ratio was investigated in chloroform using a Job plot, while a 1:1 stability constant was determined via UV–vis titration in the same solvent. Both methods raise concerns, their results lack consistency and the extrapolation of data from chloroform to aqueous systems is not justified. Additionally, theoretical calculations yielded a highly positive binding energy, erroneously interpreted as indicative of complex stability, and a questionable complex structure featuring unconvincingly short anion–tetrazine contacts. Nevertheless, functioning of reported cathode for Zn–I₂ batteries is a notable outcome of the study.

Nature, Published online: 27 October 2025; doi:10.1038/s41586-025-09791-5

Direct deaminative functionalization with N-nitroamines

Nature Communications, Published online: 23 October 2025; doi:10.1038/s41467-025-65313-x

Late-stage peripheral functionalization and structural editing of nitrogen-containing heterocycles have garnered increasing attention due to their potential for the preparation of diversifying drug-like libraries. Herein, the authors report a peripheral regioselective meta-azidation of pyridines through dearomatized oxazino pyridine intermediates, and a subsequent molecular editing step via a photo-mediated singlet nitrene insertion process.

The development of a two-stage process for converting CO₂ via CH₄ to C₆H₆ using a Ni/TiO₂ catalyst in stage 1 and a Mo/ZSM-5 catalyst stage 2. Thermodynamic calculations as well as experimentally varying parameters, aided in finding the optimal reaction conditions and reducing the coke deposition in stage 2. Furthermore, operando spectroscopy was employed to understand the increased catalyst stability in stage 2.

Abstract

In the refinery of the future, the input shifts from crude oil to biomass, plastic, and CO₂. Therefore, we need to find alternative routes to produce chemical building blocks, such as aromatics, which are used in products like, for example, fuels. In this study, we investigated a two-stage route to produce benzene from CO₂. In two sequential reactions, CO₂ is first converted into methane over a Ni/TiO₂ catalyst, and methane is further reacted to yield benzene using a Mo/ZSM-5 catalyst via the methane dehydroaromatization (MDA) reaction. Through a combination of thermodynamic calculations and experiments, we found the goldilocks conditions for performing this two-stage process. The unreacted CO₂ and H₂ from the first reaction extended the benzene production in the second reaction. Using a reaction mixture of CO₂, H₂, and CH₄ resulted in benzene production of at least 72 h, by suppressing carbon growth on the catalyst surface. However, the concentration range in which CO₂ and H₂ can be added to the feed without losing benzene production is narrow, as we show with H₂ fluctuation experiments. We demonstrate that the combination of CO₂ methanation and MDA allows us to catalytically convert CO₂ into benzene with an overall yield of 5%.

Nature, Published online: 22 October 2025; doi:10.1038/d41586-025-03416-7

Supervisors who invest in positive mentoring relationships with their PhD candidates also reap the benefits for their own research.

The use of a deep eutectic solvent (DES) in sulfonylation electrosynthesis enables the high-yield and scalable production of 2-arylsulfonylquinolines without the need of volatile organic compounds. Acting as reaction medium and removing the need of a supporting electrolyte, the DES affords excellent yields across a broad scope of compounds, allows simple water-based isolation of products, and can be efficiently reused.

Organic electrosynthesis is gaining momentum, driven by the inherent advantages of using electricity in place of stoichiometric chemical oxidants, such as the improved atom efficacy, the minimization of waste, and the lower cost. However, electrosynthesis methods rely on volatile organic solvents such as acetonitrile to solubilize the reagents, combined with expensive and nonrecyclable electrolytes, which compromise the environmental and economic viability of the approach. Taking the electrosynthesis of 2-arylsulfonylquinolines as representative case, the aforementioned issues by incorporating a deep eutectic solvent that functions simultaneously as the reaction medium and supporting electrolyte are addressed. The method delivers excellent yields, and products are isolated at gram scale via simple water washing and filtration. Interestingly, the eutectic solvent is recovered and reused for up to five cycles without significant loss in reaction yields. In a more general vein, this strategy not only eliminates volatile organic solvents throughout both the reaction and purification stages, but also integrates a recyclable solvent–electrolyte system, there for enabling a fully sustainable electrosynthetic process.

Nature, Published online: 20 October 2025; doi:10.1038/d41586-025-03346-4

Brazil, Australia and Italy have the highest satisfaction scores in Nature’s global 2025 PhD survey — but are these nations really the best places to do a doctorate?

Science, Volume 390, Issue 6770, Page 261-265, October 2025.

Methods to access 1,3-functionalized patterns from alkenes remain limited. Recently, Silvi and co-workers reported a strategy to add the methyl thianthrenium radical across alkenes to rapidly produce 1,3-dielectrophiles. The 1,3-dielectrophiles can be diversified through sequential nucleophilic substitution reactions, delivering a wide array of 1,3-functionalized products.

Abstract

Despite tremendous progress in alkene 1,2-difunctionalization, analogous methods to generate 1,3-patterns from alkenes remain limited. Recently, Silvi and co-workers reported a homologative strategy to transform alkenes into 1,3-dielectrophiles (DOI: https://doi.org/10.1002/anov.70005). They introduce a novel iodomethyl thianthrenium salt as a precursor to methyl thianthrenium radical, which adds across unactivated alkenes. Substitution of the 1,3-dielectrophiles delivers a general homologative alkene difunctionalization platform.

Through a combination of total synthesis and nuclear magnetic resonance (NMR) analysis, Aggarwal and coworkers have unveiled the stereochemical uncertainties of the complex metabolite mycapolyol E. An elegant stereoselective iterative diboration-homologation sequence has been used to build one of the longest 1,3-polyols ever constructed.

Abstract

Mycapolyol E is a cytotoxic metabolite, isolated from the marine sponge Mycale izuensis. After isolation, the stereochemistry of the 1,3-polyol fragment remained uncertain. Aggarwal and coworkers have solved this puzzle in their recent publication in Angewandte Chemie Novit through a combination of total synthesis and nuclear magnetic resonance (NMR). The total synthesis of mycapolyol E was completed in 20 steps, the longest linear sequence, using iterative diboration/homologation reactions as key transformations to assemble the complete carbon backbone with exquisite regio- and stereocontrol (https://doi.org/10.1002/anov.70003).