Themed collection 2025 Organic Chemistry Frontiers HOT articles

Molecular electrocatalysis provides a sustainable platform for C(sp³)–H activation by enabling catalyst-controlled electron transfer or atom transfer under mild conditions.

This review examines the mechanism and stereochemical outcome of substitution reactions at chiral S(VI) electrophiles.

This review systematically summarizes the photocatalytic strategies for constructing ketones from carboxylic acids and their derivatives, emphasizing single-electron radical pathways.

This review provides a systematic overview of radical-mediated C–O bond cleavage of alcohols in photocatalysis, detailing radical generation mechanisms and transformation pathways across diverse reactions.

Aromaticity-guided design of multiredox π-systems is reviewed, highlighting recent developments in mono- and polycyclic architectures. We show how the properties of such systems are controlled by the ring framework topology and heteroatom-doping.

Visible light-induced CDC offers a green and efficient method for C–C/C–X bond formation. This review highlights recent advances in visible light-mediated CDC of N-heterocycles, enabling mild, and atom-economical synthesis of valuable frameworks.

Photocatalytic radical-induced cyclization reactions offer an efficient paradigm for constructing aromatic rings due to their unique environmental friendliness, independence from electronic effects, and high functional group tolerance.

This review describes the recent progress in the development of nanosheet structures through the self-assembly of π-conjugated aromatic amphiphiles. We expect our research progress will provide a new strategy for broadening the application areas of self-assembled 2D nanosheet structures.

This work provides a comprehensive overview of recent advances in the selective transformation of diols, focusing on diverse organocatalytic strategies and the mechanistic principles underlying selectivity control.

This review covers recent advances in the synthesis and application of fluorine-containing macrocyclic peptides and peptidomimetics.

This review summarizes recent achievements in photosynthesis of vicinally functionalized organohalides through the halofunctionalization of alkenes.

The Truce–Smiles rearrangement is a powerful method for functionalizing aromatic compounds, enabling the synthesis of various (hetero)aromatic groups. This work summarizes recent advancements in this area.

Photobiocatalysis combines the advantages of photocatalytic and enzymatic processes, enabling diverse non-natural asymmetric transformations. We highlight recent advances in asymmetric photobiocatalysis categorized by light-enzyme coupling modes.

This review summarizes the latest research progress on photocatalytic reactions involving typical Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu metal catalysts, mainly focusing on the role of metals and light in the reaction process.

This review summarizes recent advances (last 5 years) in C–H halogenation via directing groups like amides, carboxylic acids, 8-aminoquinoline, N-oxides, and heterocycles, emphasizing regioselective aryl halide synthesis in modern organic chemistry.

Organocatalysis has emerged as a powerful synthetic platform for classical asymmetric multicomponent reactions, demonstrating remarkable versatility in constructing diverse molecular architectures with precise stereochemical induction.

This review discusses emerging strategies in three-component, stereoselective C–N bond-forming alkene difunctionalization, emphasizing mechanistic innovations and their impact on synthetic organic chemistry.

Katritzky's pioneering studies revealed the multifaceted cycloaddition reactivities of oxidopyridinium betaines. In this review, the follow-up research into oxidopyridinium cycloadditions and their applications are discussed.

This review summarizes the latest literature on photoredox alkene difunctionalization reactions, focusing on oxoalkylation and oxoarylation reactions, as well as CO/C–N, CO/C–P, and CO/C–O/S bond-forming procedures.

Chiral sp³-geminated bimetallic reagents based on B, Si, and Sn have drawn much attention due to their unique structure and reaction mode. This review summarizes the synthesis of nonracemic gem-borylstannyl, gem-borylsilyl, and gem-diboryl compounds.

Mechanophoric hydrogels undergo visible color changes or alterations in optical properties in response to mechanical stimuli.

The advancements in the synthesis of nitrogen-containing heterocycles via Rh(III)-catalyzed chelation-assisted tandem C–H activation/carbene insertion/annulation with diazo compounds as carbene precursors have been summarized.

This review provides an overview of recent advancements in generating N, Si, B, and C radicals through the decarboxylation of preinstalled carboxyl substrates under visible light catalysis.

Fluorinated reagents have emerged as a valuable tool in peptide chemistry. This review summarizes recent advances in polyfluorinated reagents for peptide stapling, exploring their design principles, reaction mechanisms, and biological applications.

Artificial intelligence (AI) is transforming molecular catalysis by addressing long-standing challenges in retrosynthetic design, catalyst design, reaction development, and autonomous experimentation.

We have provided a comprehensive analysis of the construction of N-containing heterocyclic compounds and their functionalization without the use of external photocatalysts, under UV/visible-light exposure in different conditions.

The recent advances on the application of electrocyclic reactions in the total synthesis of notable natural products are summarized.

Morita–Baylis–Hillman adducts have become an efficient synthon for the construction of C–C or C–heteroatom bonds, and have been widely used in the asymmetric synthesis of various new optically pure compounds.

This review focuses on the progress in catalytic asymmetric difluoroalkylation to construction of difluoroalkylated stereogenic centers. Synthetic methods, active intermediates involved and asymmetric strategies applied were summarized.

This review offers a comprehensive overview of recent advancements in the asymmetric construction of C–N bonds involving radical intermediates.

Skeletal editing enables atom-level modifications to molecular skeletons. This review highlights advances in single-atom insertions, deletions, and transmutations in (hetero)cyclic systems, offering a comprehensive view on cutting-edge strategies.

This highlight discusses the synthesis strategies and topological features of nitrogen-containing bowl-shaped polycyclic aromatic hydrocarbons.

DFT was used to investigate the possible mechanisms of NHC-catalyzed asymmetric cycloadditions between hydrazones and isatins, including [4 + 2] and [3 + 2] cycloadditions.

A novel synthesis of benzodiazepine-containing polyheterocyclics bearing a synthetically valuable vinyl substituent via C–H bond activation-initiated formal [5 + 2] annulation of 2-(indolin-1-yl)-1H-benzo[d]imidazoles with vinyl-1,3-dioxolan-2-one.

An asymmetric alkynylation reaction of prochiral terminal diynes is developed through a tandem Cu^I-mediated desymmetrising deprotonation and enantioselective addition process, furnishing products with alkyne-tethered 1,4-central chirality.

We report a chiral phosphoric acid-catalyzed polar [2σ + 2π] cycloaddition of BCBs with o-QMs. This method efficiently constructs spiro-BCHs bearing vicinal tertiary–quaternary stereocenters with excellent atom economy and high enantioselectivity.

Magnesium catalysis: A bis-guanidinate magnesium amido complex enables the first example of a substrate-assisted catalytic dihydroboration of nitriles and isocyanides, with the isolation of key intermediates and elucidation of catalytic cycles.

A chiral phosphoric acid-catalyzed kinetic resolution of racemic biaryl oxazepines with alcohols was developed, which afforded biaryl oxazepines and imidates bearing a chiral center in high enantioselectivities.

A novel bicyclic 2-pyridone (BCP) structure and a near-infrared-emissive photosensitizer based on BCP was constructed which achieving highly efficient type I photodynamic therapy.

Synthesis of chiral spiro-heterocyclic azides via asymmetric [4 + 2]-cycloaddition of conjugated vinyl azides with aurones and (E)-alkenyloxindoles mediated by chiral N,N′-dioxide/metal complexes.

Is there an oxidized version of the Wanzlick equilibrium?

Radical cross-dehydrogenative C–O coupling of oximes with hydrazones leading to fungicidal azo oxime ethers was discovered.

Electrochemically activated water mediates sustainable oxidative cleavage of both activated and unactivated alkenes without external oxidants.

A comovement group strategy is presented, which enables an orderly triple C–F bond functionalization process, providing practical access to α-ketoamides from readily available reagents by using water and oxygen in air as oxygen atom sources.

A new spirophenylacridine (SPA) derivative, SPA-SO2, was synthesized via full bridging of sulfone, carbonyl, and oxygen to the SPA core. For comparison, the characteristics of its precursor molecule SPA-S were investigated together.

The implementation of a copper-catalyzed three-component difluoroalkylamidation of alkynes has successfully enabled the rapid synthesis of structurally diverse difluoroalkylated enamide molecules.

This work establishes a mild, ambient approach for thiocarboxylation of alkenes, providing a sustainable platform for green chemistry by avoiding the use of transition metal catalysts or external reductants.

Sulfur ylides enable a stereoelectronically-assisted C–C bond insertion followed by Corey–Chaykovsky cyclopropanation or epoxidation, allowing for dual CH₂ transfer to alkenes and aldehydes.

Six oligomeric monoterpenoid indole alkaloids with new skeletons (1–6) were isolated from the flowers of Gelsemium elegans. Compound 3 alleviated inflammation and liver fibrosis, and was biomimetically synthesized.

Mild iodine(III) catalysts unlock aziridine reactivity through halogen bonding, delivering diverse N-heterocycles from challenging substrates in excellent yields.

Enantio-determining S_N2-like reductive elimination of cobalt-catalyzed radical hydroamination of alkenes with N-fluorobenzenesulfonimides has been theoretically disclosed.

The construction of aza-3D frameworks has emerged as a pivotal strategy in drug discovery, owing to their ability to mimic heteroarene bioisosteres.

An iron(III)-mediated method enables the efficient construction of naphthoselenophenes through a cascade cyclization of 1,3-diynylpropargyl alcohols and diorganyl diselenides.

An AgOTf-promoted transetherification of p-methoxybenzyl ethers with allyl and benzyl bromides is reported. It features an unusual C–O/C–Br σ-bond metathesis via an oxonium intermediate, distinct from typical C–O/O–H or C–O/C–O σ-bond metathesis.

A method involving Cu-catalyzed regiodivergent and stereoselective silylation of 2,3-disubstituted 1,3-dienes is developed, delivering 2,1-, 4,1-protosilylation and 4,1-borosilylation products with high levels of scope, scalability and practicality.

A highly efficient asymmetric allenylic alkylation for the construction of 1,3-nonadjacent allenyl axial and central chirality through synergistic Ni/Pd catalysis.

Enantioselective construction of cycloalkyl amines with two adjacent chiral centers via transannular directed, NiH-catalysed cycloalkene desymmetric hydroalkylation.

DFT calculations reveal the Ni–Al cooperative mechanism in C–P bond activation, emphasizing the role of AlMe₂Cl in stabilizing transition states, the effect of PPh₃ on efficiency, and the influence of substituents.

A protocol for synthesizing all-carbon bicyclo[3.1.1]heptanes (BCHeps) through palladium-catalyzed dipolar (3 + 3) cycloadditions of bicyclobutanes (BCBs) with vinylcyclopropanes has been developed.

A visible-light catalyzed strategy for remote C(sp3)–H alkylation of 1-(o-iodoaryl)alkan-1-ones with N-(arylsulfonyl)acrylamides has been reported via a 1,5-hydrogen atom transfer (HAT), 1,4-aryl migration, and SO2-extrusion sequence.

The first catalytic enantioselective Urech synthesis is developed via organocatalytic desymmetrization and kinetic resolution. Using easily available malonic esters and isothiocyanates as substrates, various hydantoins with aza-quaternary stereocenters are formed under simple conditions.

Radical transnitrilation of arylborons via a mild copper catalysis was developed, featuring broad scope, high functionality tolerance, scalability and practicality.

A CF₃CHN₂-extended 1,3-diiodination through interrupted alkene diiodination with carbon atom insertion under visible light was achieved for the synthesis of trifluoromethylated 1,3-diiodides.

A straightforward and green electrosynthesis of indole-fused polycyclics through radical domino couplings was developed.

Herein, B–H and N–H insertion reactions of iodonium ylides in the presence of an iron catalyst complexed with imidazo[1,5-a]pyridine are developed, achieving the borylation and amination of 1,3-dicarbonyl derivatives under mild reaction conditions.

An iron-catalyzed carboazidation of alkenes for the regioselective synthesis of multi-substituted cyclobutylamines was reported.

A novel method enables inter-/intramolecular benzannulation to synthesize PAHs have been disclosed. Experimental and DFT data confirm the TDRA's role in the HAA step of enolized 1,3-dicarbonyls via asynchronous PCET.

We report a photoredox-catalyzed multicomponent coupling of styrenes, isocyanides, and RAEs, enabling the efficient synthesis of diverse pseudo-4-component adducts.