Polycyclic heterocycles are prevalent in medicines, functional materials and natural products, making their synthesis a significant focus in modern organic chemistry. Herein, we present a Lewis acid-mediated cascade annulation of 1,6-enynols with o-aminobenzonitriles for the chemoselective synthesis of oxepino[3,4,5-de][1,6]naphthyridine and chromeno[2,3,4-de][1,6]naphthyridine derivatives. This reaction design enables selective control over the carbon-heteroatom and carbon-carbon bond formation in an efficient, atom-economical manner, allowing the one-step synthesis of rare [6-6-7] and [6-6-6] core polycyclic heterocycles containing three heteroatoms. Density functional theory (DFT) calculations and control experiments reveal that the reaction’s high selectivity is achieved by modulating the reactivity of electron-rich alkenyl groups in the enynols, which selectively directs the intramolecular dehydroaromatization and cyclization processes.

2,2'-Dihalo-1,1'-binaphthyl compounds can introduce coordinating groups and other complex functional systems into the binaphthyl skeleton; however, their structural diversity renders preparation challenging. In this study, a streamlined approach is developed to prepare dihalobinaphthyl compounds that uses designed, easily obtained α-hydroxyl haloalkynes as the starting materials, which combine activity of haloalkynes and traceless directional hydroxyl groups. This process involves a palladium-catalysed 1,2-halo shift, electrophilic carbocyclisation, dehalogenative coupling with another α-hydroxyl haloalkyne, and halogenated electrophilic cyclisation. Density functional theory calculations shows the occurrence of 1,2-halo shift is primarily governed by the coordination of the aromatic ring in the palladium catalyst. The target 2,2'-dihalo-1,1'-binaphthyl compounds can be prepared on the gram scale, and afford a series of ligands, catalysts, and high-value binaphthyl-based materials. This method will significantly expand the synthetic toolbox for dihalobinaphthyl compounds and create possible opportunities for preparing functionally diverse binaphthalene-based architectures with tailored properties.

A novel visible light-catalyzed strategy for single-carbon-atom skeletal editing of acyclic electron-deficient alkenes has been developed. This method offers an efficient approach for the high-value transformation of α,β-unsaturated ketones into multifunctionalized furan skeletons by employing α-iodonium diazo compounds as carbyne precursors under photoredox conditions.

Sulfone polymers are amorphous aromatic thermoplastics in which each repeating unit contains a sulfone group connected to phenylene rings by aryl ether linkages. This architecture imparts high glass transition temperatures, resistance to oxidation and hydrolysis, dimensional stability, and transparency, and has established bisphenol A polysulfone (PSF), polyethersulfone (PES), and polyphenylsulfone (PPSU) as mainstays of the specialty engineering plastics market. Existing reviews consider sulfone polymers either as membrane materials or primarily from a synthetic perspective; the complete manufacturing chain from sulfur feedstock to a finished high-end component has not been examined systematically. This review covers literature published from 2015 to 2026 and is organized around this value chain. We first analyse the industrial state of the art by examining chlorosulfonation, the sulfuric acid and sulfur trioxide routes to 4,4′-dichlorodiphenyl sulfone, and one- and two-step solution polycondensation to PSF, PES, and PPSU. We conducted a comprehensive comparison of these process routes. The resulting bottlenecks define the central theme of the review: green synthesis. At the monomer stage, we assess solvent-free and recyclable-acid sulfonylation, sulfide oxidation with H2O2 and O2/air, palladium-catalyzed C–H sulfonylation, and solid sulfur dioxide surrogates that valorise surplus industrial sulfur. At the polymer stage, we assess ionic-liquid and zwitterionic media, phase-transfer catalysis, AB-type self-polycondensation, continuous and process-intensified polymerization, melt polycondensation, and oxidative conversion of poly(arylene sulfide)s, and identify opportunities to integrate monomer-level and polymer-level green chemistry. Modification strategies, including blending, copolymerization, grafting, and stimuli-responsive functionalization, are then linked to the high-end applications that now drive demand: proton- and ion-exchange membranes, water treatment, gas separation, haemodialysis, and epoxy toughening. Finally, we identify the most promising strategies and current best-performing materials, analyze the origins of the remaining bottlenecks, and outline research priorities and translational pathways for moving these technologies from the laboratory to industrial deployment.

We have developed an efficient and concise synthetic strategy for the rapid construction of morpholine-fused bicyclic scaffolds under mild aerobic conditions via Pd(II)-catalyzed oxidative cyclization of 1,3-cyclohexadiene with amino alcohol substrates. This protocol enables direct 1,2-aminooxygenation of cyclic dienes, providing access to a range of fused morpholine derivatives with good regioselectivity and yields.

A palladium-catalyzed regioselective cascade alkynylation of diaryl ethers in basic ionic liquid C(sp2)-O bond cleavage for the assembly of structurally diverse aryl internal alkynes is described. In the presence of 1 mol% of IPrtBu-Pd-Cin-Cl as the catalyst and the ionic liquid [Apmim]BF4 as the solvent and the base, a wide variety of terminal alkynes and diaryl ethers could be excellently tolerated. This alkynylation protocol features good yields (up to 94%), excellent functional group compatibility (40 examples) and a green synthetic process. Notably, the robustness and potential of this approach have also been successfully certified by the valorization of polyphenylene oxide wastes, gram scale experiment, recycling experiment (6 times), and late-stage modification of pharmaceuticals.

Despite the significant potential of chiral sulfinamides in drug discovery, the stereocontrolled synthesis of such molecules remains a formidable challenge. Herein, we report a nickel-catalyzed regio- and enantioselective hydrosulfinamidation of readily available aryl alkenes that provides efficient access to diverse chiral sulfinamides bearing two contiguous stereocenters. This method exhibits broad functional group tolerance, complete regioselectivity, and excellent enantioselectivity (up to 98% ee). The reaction is readily scalable to gram quantities, and the resulting products can be further transformed into a variety of sulfur-containing compounds with full retention of enantiopurity. Mechanistic studies elucidate the radical reaction pathway and rationalize the origins of regio- and enantioselectivity. The process commences with the regio- and enantioselective syn-hydronickelation of the alkene by an in situ-generated Ni(II)-H species, yielding an alkylnickel intermediate. Subsequently, a turnover-limiting step occurs through 2,3-addition of the alkylnickel species across the S═N bond of the sulfinylamines.

A photoredox-catalyzed Csp3-H carbynoid functionalization of 1,3-dicarbonyl compounds with α-iodionium diazo compounds has been developed to rapidly assemble α,β-diacyl-α,β-unsaturated ketones. This protocol offers a straightforward approach to access β-deuterated-α,β-unsaturated carbonyl molecules via a 1,2-H shift process.

A straightforward strategy for the electrochemical amidation of benzyl halides via radical-polar crossover has been developed. The reaction was carried out with acetonitrile as both the solvent and the amidation reagent and (PhS)2 as a "radical shuttle". Various N-substituted acetamide products can be afforded from benzyl halides under metal- and oxidant-free electrochemical conditions. This method involved a reduction pathway and employed paired electrolysis, featuring high electron economy. Meanwhile, it also has the features of simple operation and mild reaction conditions.

A palladium-catalyzed reductive carbonylative benzannulation of 1,4-enynes with carbon dioxide (CO2) as carbonyl source has been developed for the first time, offering an efficient approach to a wide range of multi-substituted phenols in high yields. The success of this transformation hinges on a synergistic dual silane reduction system: one silane acts as a reductant for the conversion of CO2 to CO, while the other serves as a hydrogen source to generate Pd-H species. This method is operationally simple, exhibits broad substrate scope, and can be applied to the late-stage modification of complex pharmaceutical molecules as well as the synthesis of bioactive compounds such as thymol.

Herein, we report a novel strategy for the synthesis of 3-(1H-indol-3-yl)isoindolin-1-ones via copper-mediated dual cyclization of 2-(alkynylaryl)anilines with 2-formylbenzonitriles. Mechanistic studies reveal that the isoindolinone core is preferentially formed, and this transformation involves an unexpected isoindolinone migration process. This approach features high atom economy, broad substrate scope, and the use of inert nitrile as the nitrogen source for isoindolinone. Moreover, the practicality of this method is demonstrated by gram-scale synthesis and late-stage derivatizations.

3,6-Dihydro-2H-pyran heterocyclic framework is one of the currently developed heterocyclic building blocks in both pharmaceutical chemistry and organic synthesis, but with significant challenges. To overcome these challenges, herein, we report a robust synthetic methodology of palladium-catalyzed carboetherification of alkenes with alkynols for accessing polyfunctionalized 3,6-dihydro-2H-pyrans under aerobic oxidative conditions. In particular, this synthetic approach features excellent functional group compatibility, mild reaction conditions, and good step- and atom-economy. Additionally, an array of functional groups such as halogen group, ester, nitrile, aldehyde, phenoxy, and aromatic heterocycles were nicely tolerated, affording the synthetically challenging 2H-pyran derivatives in moderate-to-good yields. Notably, the practicability of this protocol is further verified by gram-scale synthesis and the late-stage diversification of pharmaceuticals and biologically active molecules.

An innovative [2+1+1+1] cyclization of trifluoroacetamides, haloalkynes and isocyanides for the synthesis of 2,5-diaminopyrrole derivatives under palladium catalysis is described. This novel procedure exhibits broad substrate scope with great functional group tolerance, excellent chemo- and regio-selectivities as well as high efficiency in bond formations, in which two carbon-carbon double bonds and two carbon-nitrogen single bonds were built in one step. Applications of the method are verified by the late-stage modification of bioactive molecules, as well as the construction of functional pyrroles and pyrroloindolines from the derivatizations of the aminopyrrole products, which show the potential utilities in medicinal chemistry and materials science. In addition, DFT calculations elucidate that the reaction might undergo a key isomerization promoted consecutive isocyanide insertions at different site.

The selective oxidative amination of alkenes, particularly dienes bearing multiple reactive sites and modes, represents an attractive approach for constructing nitrogen-containing motifs. However, precise control over regioselectivity (Markovnikov/ anti-Markovnikov and branched/linear), the amination sequence, and stereoselectivity remains challenging, especially for primary amines. Herein, we report a cooperative noncovalent interaction-directed strategy that leverages pi-pi stacking and hydrogen bonding to enable branch-selective allylic C-H amination of alkyl dienes with primary amines, facilitating subsequent aza-Wacker oxidation or a second allylic C-H amination. Divergent cyclization enables the streamlined synthesis of pyrrole, pyrrolidine, and tetrahydroindole scaffolds via dual C-H amination (>100 examples). Mechanistic and computational studies reveal that pi-pi stacking-induced orientation of the alkene chain, together with the interplay between the coordination and hydrogen-bonding properties of the anionic ligand, is critical for the efficiency and selectivity of the amination process.

As an abundant and renewable C1 source, CO2-involved organic synthesis stands for green and sustainable chemical transformations, which have been well developed in the past decades. Diverse reactions are realized via C–X (X=C, N, O) bond formation, providing various organic compounds with high selectivity and efficiency. In recent years, a variety of novel organic transformations with CO2 have emerged under different reaction systems, especially with the renaissance of photochemistry and electrochemistry. This review will summarize the advances in CO2-involved organic synthesis in the past five years. The content is organized based on the chemical bond formation in the organic transformation with CO2, mainly including C–C bond, C–N bond, and C–O bond formation.

The alpha, beta-butenolide moiety serves as a valuable electrophile in Michael additions and cycloadditions, enabling the direct and atom-economical construction of gamma -butyrolactones-a unique structural motif prevalent in natural products. However, its susceptibility to aromatization limits its applications in complex natural products synthesis. Herein, we report the asymmetric synthesis of (-)-14-epi -sinugyrosanolide A, a stereoisomer of the natural product sinugyrosanolide A, in which the aromatization of alpha, beta-butenolide moiety was inhibited. A mild acid-promoted intramolecular [5 + 2] cycloaddition could rapidly assemble the synthetically challenging 5,5,7,6 core found in several Sinularia diterpenoids. The key cycloaddition precursor was prepared through an unconventional sequence involving an aldol reaction of dihydropyranone acetal derivatives and aldehyde, followed by ring-closing metathesis (RCM). This research not only accomplishes the asymmetric synthesis of (-)-14-epi -sinugyrosanolide A, but also shows its potential for synthesizing other cembranoid and norcembranoid natural products. More importantly, it establishes an alternative approach toward synthesizing structurally complex molecules containing gamma -butyrolactone moiety.

Despite the broad utility of γ-amino alcohols, their direct and diverse synthesis from cheap, abundant feedstocks remains challenging. Here, by developing a bifunctional single-atom cobalt catalyst supported on hierarchical ordered porous carbon matrix (Co-N4/HPC), it enables hydroxyaminomethylation of nonactivated terminal alkenes with nitroarenes and formaldehyde using HCOOH reductant. This difunctionalization reaction features operational simplicity, high atom/step economy, broad substrate scope, excellent functionality tolerance, high selectivity, and catalyst reusability, offering a practical platform for the general synthesis of γ-arylamino alcohols from bulk chemicals. Notably, the Co-N4 sites mediate mild reduction, while the mesoporous N-doped carbon support enriches formaldehyde via physical adsorption, facilitating the capture of hydroxylamines formed in situ from nitroarene reduction. Subsequent 1,3-dipolar cycloaddition of the resulting nitrones with alkenes, followed by reduction of the cycloadducts, delivers the desired products. The concept of exploiting metal-support synergy for mild reduction and efficient intermediate conversion will open a door to the further development of useful tandem reactions through rational catalyst design.

A metal‐free photoredox catalysis enabling a decarboxylative radical cascade cyclization for the efficient synthesis of 2‐alkylbenzothiazoles/2‐alkylbenzoselenazoles is described. This protocol utilizes alkyl N‐hydroxyphthalimide (NHPI) esters and 2‐isocyanaryl thioethers/selenoethers as the substrates, and the transformation proceeds through a photoredox‐catalyzed, radical addition‐triggered cascade cyclization. This method features mild conditions, excellent functional group tolerance, and a broad substrate scope encompassing primary, secondary, and tertiary alkyl radicals, providing a versatile entry to these valuable heterocycles.

Chiral amines are privileged chiral building blocks with extensive applications in pharmaceuticals, advanced materials, and asymmetric catalysis owing to their unique structural features and functional diversity. Although palladium-catalyzed asymmetric allylic C-H amination offers an efficient strategy for constructing these motifs, the simultaneous challenges of coordinating sterically hindered internal alkenes and suppressing catalyst deactivation by Lewis basic amines have severely limited the development of asymmetric oxidative amination systems. In this study, we disclose a novel ester, an unmodified native functional group-directed strategy that enables the palladium-catalyzed asymmetric oxidative allylic amination of internal α,β-unsaturated esters with basic amines. This protocol yields a diverse array of non-natural γ-amino acid derivatives with excellent yields and high enantioselectivity (93% to >99% e.e.). Comprehensive mechanistic investigations, incorporating controlled experiments and density functional theory calculations, elucidate the intricate reaction pathway. The synthetic utility is further demonstrated through various product derivatizations and the streamlined synthesis of bioactive compounds. This work establishes a general platform for accessing enantioenriched nitrogen-containing architectures from readily available alkenes and amines.

Binaphthalene ligands and catalysts play a pivotal role in the development of modern chemistry. In contrast to 1,1 '-binaphthyl, the 1,2 '-binaphthyl framework has received comparatively little attention from chemists. In this study, a streamlined approach was developed for the preparation of 1 ',2-dihalo-1,2 '-binaphthylene derivatives (28 examples) via a concise two-step, one-pot strategy. Specifically, this method employed readily available alpha-hydroxy haloalkynes to directly construct the 1 ',2-dihalo-1,2 '-binaphthylene framework. The high step economy substantially enhanced the overall efficiency of accessing these valuable scaffolds. Additionally, 1 ',2-dihalo-1,2 '-binaphthylene was prepared on the gram scale and afforded a series of ligands, catalysts, and high-value 1,2 '-binaphthyl-based materials. The inherent asymmetry of the 1,2 '-binaphthyl framework allows for more versatile designs of binaphthyl ligand catalysts, thereby providing an approach for the development of efficient binaphthyl ligands and binaphthyl catalysts.