Herein, we describe a direct route for the synthesis of 3- gem-difluorovinyl lactams through Zn-mediated reductive hydrodehalogenation. Importantly, by using inexpensive deuterium oxide (D ₂O), the high value-added vicinal dideuterated  gem-difluoroalkenes with excellent deuterium (D) incorporation were prepared. Mechanism studies indicated a successive single electron transfer process: the reaction initially undergoes hydrodechlorination to give the intermediate  α-trifluoromethylidene lactams, which are then activated by the  in-situ generated zinc cations and reduced to the desired product  via hydrodefluorination.

Chiral 1, 3-substituted fragments are ubiquitous in pharmaceutical molecules and natural products, prompting the development of numerous methods to access these structures. Nonetheless, devising synthetic routes for complex chiral architectures in practical applications typically demands years of expertise. Herein, we developed a nickel-catalyzed enantioselective migratory arylboration reaction of allylboronic esters using a chiral 1, 2-diamine ligand, yielding a range of chiral 1, 3-bis(boronates) with high enantioselectivity. The protocol is characterized by its use of commercially available substrates, mild reaction conditions, user-friendly procedures, and a broad substrate compatibility. Moreover, we demonstrate the practicality and application potential of this reaction by synthesizing several key drug intermediates.

Six new acorane-type sesquiterpenes, named penijanacoranes A—F ( 1— 6), as well as one known eudesmane sesquiterpenoid 1 α, 6 β, 11-eudesm-triol ( 7) have been isolated from a deep-sea-derived fungus Penicillium janthinellum SH0301. Their structures and absolute configurations were established by the comprehensive spectroscopic analysis, TDDFT-ECD calculations, and X-ray diffraction. Penijanacorane A ( 1) was identified as a rare acorane-type sesquiterpene lactone featuring a novel 6/5/6 tricyclic system, while penijanacoranes E and F ( 5 and 6) represented undescribed examples of nor-acorane sesquiterpenes at C-1. Penijanacorane C ( 3) exhibited significant inhibitory activity against LPS-induced NO production in Raw264.7 macrophages with an IC ₅₀ value of 6.23 µM, which was more potent than that of positive control dexamethasone (IC ₅₀ = 11.49 µM). This study expanded the chemical diversity of acorane-type sesquiterpenoids and revealed that compound 3 was a potential molecule for anti-inflammatory agents.

The direct reductive coupling of carbonyl compounds with propargyl halides is a powerful and reliable tool in the synthesis of α-allenols. However, stoichiometric metal reductants, harsh reaction conditions and a variety of additional additives are required in the traditional strategies. Additionally, the reactivity and regioselectivity control remains an elusive challenge. Herein, we developed the Ti-catalyzed regioselective reductive coupling of readily available aldehydes and racemic propargyl bromides to rapidly access a wide range of α-allenols. This method proceed efficiently in a reductive radical-polar crossover manner featuring mild conditions, excellent regioselectivity control, broad substrate scope, and eco-friendliness. Preliminary mechanistic studies support the radical-involved catalytic cycle. And the DFT calculations demonstrate that the regioselectivity is determined by the Zimmerman-Traxler-type transition states.

Real-time on-site monitoring of resorcinol (RS) concentrations is crucial for detecting hazardous levels, enabling prompt response measures to mitigate potential environmental and health risks. In this study, we developed an innovative method using CoNi@CN-2 nanozymes to activate peroxymonosulfate (PMS) for oxidizing 3, 3′, 5, 5′-tetramethylbenzidine (TMB). Our results show that the formation of Ni ²⁺ through the oxidation of Ni ⁰ on the CoNi@CN-2 surface significantly enhances the electron-donating capacity of Co ⁰. The catalytic reaction of TMB is mediated by redox active species (SO ₄ ^•-, •O ₂ ^-, •OH and  ¹O ₂). RS drives colorimetry by transferring electrons to the benzene ring and specific nitrogen atoms in ox-TMB, reducing ox-TMB to TMB. Furthermore, the colorimetric assay shows a robust linear correlation between RS concentration and absorbance (Abs), described by Abs = -0.44[RS] + 0.886 (0—200 µmol/L, R ² = 0.983). Also, we introduce a novel smartphone-integrated autonomous detection software that can analyze RS concentration and grayscale values (GSV), yielding GSV = 0.327[RS] + 63.601 (0—200 µmol/L,   R ² = 0.990) with a detection limit of 5.29 µmol/L. Additionally, excess PMS leads to ROS attacking specific sites in ox-TMB, forming secondary oxidation products. This study has enabled rapid and accurate detection of RS, making a significant contribution to environmental safety and protection.

Alkenylsulfonates are commonly encountered in medicinal chemistry, polymer chemistry, and organic synthesis. In this research, an electrochemical reaction involving alkynes, NaHSO ₃, and alcohols has been developed. This method yields functionalized alkenylsulfonates in good yields with broad functional group tolerance. Mechanism studies indicate that anodic oxidation of inorganic sulfite, radical insertion process, and HAT process are involved in this transformation.

Single-atom catalysts (SACs) have attracted significant attention due to their high atomic utilization and tunable coordination environment. However, the catalytic mechanisms related to the active center and coordination environment remain unclear. In this study, we systematically investigated the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalytic activities of NiN ₄, NiN ₃, NiN ₃H ₂, NiN ₄X, NiN ₃X, and NiN ₃H ₂X (X denotes axial ligand) through density functional theory (DFT) calculations. This study unveils two distinct reaction pathways for ORR and OER, involving proton-electron pairs adsorbed from both the solution and the catalyst surface. The overpotential is the key parameter to evaluate the catalytic performance when proton-electron pairs are adsorbed from the solution. NiN ₃ and NiN ₃H ₂ show promise as pH-universal bifunctional electrocatalysts for both ORR and OER. On the other hand, when proton-electron pairs are adsorbed from the catalyst surface, the reaction energy barrier becomes the crucial metric for assessing catalytic activity. Our investigation reveals that NiN ₃H ₂ consistently exhibits optimal ORR activity across a wide pH range, regardless of the source of proton-electron pair (solvent or catalyst surface).

Photocatalytic aerobic oxidative desulfurization (PAODS) is a sustainable alternative technology to traditional, energy-intensive fuel desulfurization methods. Nonetheless, its advancement is hindered by the notable challenge of inadequate electron-hole separation efficiency within the existing catalytic systems. Herein, a Janus 2D/2D heterostructure composed of Co ₃O ₄ and CoMoO ₄ is reported for the PAODS of thiophenic sulfides. Through a combination of detailed experimental characterizations and density functional theory (DFT) calculations, we elucidate the formation of a type II p-n heterojunction in the catalyst, significantly enhancing electron-hole separation through electric field force and reducing the possibility of electron-hole recombination due to the spatial separation of redox centres. The photocatalyst exhibits exceptional activity and demonstrates an impressive performance of 10.4 mmol·g ^-1·h ^-1 in the oxidation of dibenzothiophene (DBT). Moreover, the photocatalyst demonstrates profound desulfurization capabilities in real diesel, reinforcing its promising prospects for industrial application. These discoveries provide invaluable insights, both scientifically and practically, towards the development of advanced photocatalysts for PAODS processes.

Comprehensive Summary: Indolizine is a nitrogen-containing heterocycle with strong aromaticity, possessing a delocalized 10π-electron system. Based on the indolizine scaffolds, numerous molecules with biological activity and organic functional materials have been synthesized. Since 2016, over 110 papers have been published on the synthesis of indolizine scaffolds, but the reviews on synthesizing indolizine scaffolds have been incomplete and not up-to-date. Herein, from the perspective of the structure of indolizine with the combination of pyrrole and pyridine ring, we focus on the construction of indolizine scaffolds through the diversity of starting substrates, including pyridine derivatives (N1-substituted pyridinium salt derivatives, C2-substituted pyridine derivatives, N1- and C2-free substituted pyridine derivatives), pyrrole derivatives and unoriginal ring substrates. Furthermore, the corresponding reaction mechanisms of synthetic methodologies are also elaborated. Therefore, this review not only paves the way for indolizine synthesis but also provides insight into exploring new reaction modes for constructing nitrogen-containing heterocycles.

Key Scientists: Indolizine was discovered by Angeli in 1890 and first prepared by Scholtz in 1912 from α-picoline and acetic anhydride. A general approach was developed by Chichibabin in 1927, that is of practical value for the preparation of 2-alkyl- or 2-arylindolizines. The Chichibabin reaction was the ring closure of quaternary pyridinium halides. At the begining of the 21st century, Basavaiah introduced a new dimension in the Baylis-Hillman chemistry leading to a novel facile convenient methodology for synthesis of indolizine scaffolds in one-pot operation. In 2010, Barluenga reported Cu(I)-catalyzed regioselective [3+2] cyclization of unsubstituted pyridines toward alkenyldiazoacetates leading to functionalized indolizine derivatives, that was the first successful example of metal-catalyzed cyclization of a π-deficient heterocyclic system with alkenyldiazo compounds. In 2019 and 2022, Xi and Liu exploited the methods of non-pyridine derivatives as starting materials to synthesize indolizines, respectively. In 2022, Guo developed an environmentally benign electrooxidative approach for constructing formyl- and acyl-substituted indolizines.

The extensive use of plastics, valued for their lightweight, durability, and cost-effectiveness, has led to severe environmental pollution, with 72% of plastic waste ending up in landfills or natural habitats. Traditional methods for plastic decomposition, including both mechanical and chemical approaches, often face challenges such as incomplete degradation and stability concerns. The innovative concept of mechanical gating presents a promising solution by incorporating mechanophores into polymer structures, enabling controlled degradation. Recent advancements have focused on utilizing mechanophores, such as cyclobutane, as "door locks" to regulate the degradation process. This perspective highlights recent progress in this field, demonstrating the potential of mechanophore-based strategies for achieving on-demand polymer degradation. It addresses the limitations of conventional recycling methods and explores how this approach can balance polymer stability with environmental degradability, paving the way for more sustainable plastic management solutions.