A 1,1-hydroboration of alkynylgermanes with unique trans-Ge/B stereochemistry under transition-metal-free conditions is reported. Mechanistic studies suggest that a pathway involving α-boration followed by a stepwise 1,2-Ge/H shift on the intermediate structurally lies between an alkyne–Ge⁺ π complex and a typical vinyl cation. The resulting Ge/B bimetallic modules, along with a Ge*/Ge/B trimetallic variant, can be conveniently transformed into trisubstituted olefins through iterative divergent cross-coupling. This work demonstrates that incorporating metalloids into classical organic reactions may offer unconventional chemical selectivity and efficient synthetic applications.

Due to their modularity and conciseness, atroposelective cross-coupling is one of the most attractive approaches for synthesizing axially chiral binaphthyl molecules. While transition metal-catalyzed cross-couplings provide reliable synthetic strategies, alternative methods that accommodate a broader range of substrates without their pre-functionalization are highly beneficial. Here, we demonstrate that using the bifunctional organocatalyst (DHQD)₂PHAL enables atroposelective cross-coupling of 2-naphthols and diaryliodonium salts with high efficiency, and yields (up to 72%) and excellent enantioselectivity (up to >99% enantiomeric excess). Further transformations of the products highlight the versatility of other binaphthyl compounds while maintaining their axial chirality.

Azulene-type polycyclic hydrocarbons have recently attracted a great deal of attention from researchers; however, their structure–property correlations and possible uses are not being fully explored due to the lack of effective synthesis techniques. Herein, we report a hitherto unexplored one-pot, microwave-assisted synthetic strategy toward diverse tribenzo[a,f,h]azulen-10-ones by tandem Suzuki coupling and a subsequent cyclo-condensation process. The strategy provides tribenzo[a,f,h]azulen-10-ones in good to excellent yields with structural versatility, including thiophene-embedded tribenzo[a,f,h]azulen-10-ones. In addition, UV–visible absorption studies have been used to investigate their structural and photophysical properties. This strategy offers a new platform for promptly synthesizing numerous unexplored azulenone units.

A visible-light photoredox [3 + 2] cycloaddition reaction of arylidenecyclopropanes with olefins was developed, employing the readily available and commercially accessible TMSN₃ as an efficient radical mediator. This method provides a convenient and efficient route to arylidenecyclopentanes from readily available starting materials, is metal-free, and features enhanced atom and step economy, excellent selectivity, extensive substrate versatility, favorable functional group compatibility, structural diversity, and mild reaction conditions, which further enable late-stage diversification. DFT calculations elucidated that this transformation entails sequential radical generation, radical addition, ring-opening, radical cyclization, and elimination steps.

This study reports the first self-ring-opening reaction of a novel eight-membered heterocyclic skeleton, dibenzo[b,f][1,5]diphosphacyclooctatetraene (PCOT), into (Z)-alkenyldiphosphines, which involves the sequential cleavage of two phosphonium–ylide bonds and the formation of a C═C bond. Theoretical analyses further rationalize the stereoselective formation of Z-form products and the chemical driving force behind the phosphonium–ylide (P¹═C¹) bond cleavage. This work represents the first example of π-conjugated eight-membered phosphacycles featuring two internal phosphonium–ylide bonds and their self-ring-opening rearrangement.

We report a transition metal-free aryne Alder-ene (AAE) reaction of conformationally locked styrenes like methylene indane (5,6-fusion) and methylene tetralin (6,6-fusion) to provide aryl-decorated indenes and dihydronaphthalenes. DFT studies compared the transition states between 5,6- and 6,6-fused systems. The synthetic utility of the 5,6- and 6,6-fused products was demonstrated.

An efficient and practical electrochemical method for synthesizing fluorothioformate derivatives, an underexplored functional group, is reported. The strategy is based on the anodic decarboxylation of oxalic acid monothioesters, which rapidly generates highly reactive alkyl (oxomethylidene)sulfonium intermediates. These intermediates are effectively trapped by the inexpensive and commercially available triethylamine trihydrofluoride (Et₃N·3HF), which acts as both a nucleophilic fluoride source and a supporting electrolyte, leading to the formation of the desired fluorothioformates. This methodology enables the rapid and scalable synthesis of fluorothioformate derivatives, enabling their broader exploration in organic chemistry. In particular, these compounds can be readily and selectively converted to S-thiocarbamates and urea derivatives in a one-pot process through reactions with amines, demonstrating their synthetic utility. The scalability of this electrochemical fluorination was validated, showing no loss of yield. Cyclic voltammetry studies were carried out to shed some light on the mechanism of these novel transformations.

A rhodium-catalyzed enantioselective C–H germylation reaction was developed, enabling the synthesis of germepin derivatives with diverse substitutions. This study represents a rare application of E–H/C–H (E = Si or Ge) dehydrogenation coupling reactions in synthesizing inherently chiral molecules, marking the first successful enantioselective synthesis of inherently chiral seven-membered heterocycles containing group 14 elements. Compared to their structurally analogous tribenzosilepins, tribenzogermepins exhibit enhanced stereochemical stability under the reaction conditions. Furthermore, the compatibility of the Si–H bond under identical conditions highlights the distinct reactivity of Si–H and Ge–H bonds.

Carbonyl-containing compounds serve as essential building blocks in various synthetic processes. However, due to the high bond energy of the C═O double bond, the traditional deoxygenation methods often require harsh conditions or toxic reagents. Direct carbonyl deoxygenative coupling of aldehydes and ketones is still challenging under mild conditions. Herein we report the successful establishment of an electroreductive coupling strategy utilizing aromatic carbonyls and terephthalonitrile. A key component of our approach is the use of closo-boranes, specifically (Et₄N)₂B₁₀H₁₀, which serve as an in situ deoxidant by single-electron oxidation.

Herein, we report a modular α-monoalkylation of cyclic 1,3-dicarbonyls with cyclopropyl alcohols through a cyclic iodonium ylide strategy. This approach is general, base-free, operationally simple, and suitable for various medically important (hetero)cyclic 1,3-dicarbonyls. A wide range of cyclopropyl alcohols, easily prepared from feedstock chemicals, can serve as modular and complement alkylating agents. Importantly, the newly formed carbonyl groups in the resulting products provide a versatile platform for numerous synthetic applications.

Dithioesters are important agents for chain transfer in polymer chemistry and precursors in the synthesis of heterocycles. Straightforward approaches to their synthesis are therefore in demand. Outlined herein is a method to access such compounds in one-pot. 2-Aryl-1,3-dithiolanes undergo ring fragmentation with LiHMDS in CPME to generate aryl-dithiocarboxylates in 5 min at 100 °C. These anions are subsequently captured in the second step by addition of various alkyl halides and diaryliodonium salts to furnish a large library of dithioesters in good yields. The method can be also employed in a one-pot, one-step manner for alkyl bromides and allows the synthesis of dithioesters in gram scale.

We report herein the palladium-catalyzed Hiyama cross-coupling of heterocyclic phosphonium salts with diverse (hetero)arylsilanes through C–P bond cleavage, providing an alternative approach for the highly regioselective functionalization of pyridines and relevant nitrogen-containing heterocycles. This silicon-based protocol is amenable to gram-scale synthesis and also applicable to the late-stage functionalization of pharmaceutically relevant complex molecules.

This study reports the catalytic N-methylation of NH-sulfoximines using carbon dioxide (CO₂) under metal-free conditions. A mesoionic N-heterocyclic olefin (mNHO) was used as a catalyst for the N-methylation of NH-sulfoximines in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN) under mild conditions. This process was used to convert various NH-sulfoximines into N-methylsulfoximines. This protocol was also applicable for the synthesis of ¹³C-labeled N-methylsulfoximines using ¹³CO₂. A mechanistic cycle was proposed by performing a series of control reactions and successfully characterizing active catalytic intermediates by either single-crystal X-ray or NMR spectroscopic studies.

Herein, we disclose a manganese-catalyzed approach that enables the direct iododiborylcarbofunctionalization of alkynes with a (diboronmethyl)iodide under mild conditions. This approach grants access to a range of structurally unique and synthetically useful γ-iodine-substituted gem-bis(boronate)s, which have hitherto been inaccessible. This atom-economical strategy displays excellent functional-group tolerance, encompasses a wide range of applicable substrates, and demonstrates a high Z:E selectivity (up to 96:4).

Protein phosphorylation is a very important post-translational modification that regulates diverse cellular activities. In addition to classic monophosphorylation, there is also oligophosphorylation from pyrophosphorylation to polyphosphorylation. Moreover, organophosphates may modify residues such as via AMPylation and ADPylation. Although plenty of new types of protein phosphorylation have been revealed, molecular mechanisms of the biological functions are still challenging to study due to the lack of a good method to prepare proteins of interest with such site-specific PTMs. Here we report a facile method to install inorganic and organic phosphates on peptides and proteins. Vinylaryl sulfonium with an electron-withdrawing group was applied to cysteine alkylation and subsequent cyclization by γ-sulfur yielding episulfonium. This highly electrophilic intermediate was later attacked by a phosphate reagent to yield site-specifically phosphorylated cysteine peptides and proteins. As a result, this method does not require a special precursor residue on peptides/proteins or activation of phosphate reagents. In addition, this method is applicable to diverse inorganic phosphates and organophosphate. Therefore, we believe that this method will accelerate protein phosphorylation research by simple preparation of site-specific modified proteins. We also believe it offers a simple bioconjugation strategy via a phosphate linker.

The integration of trifluoroacetyl (CF₃CO) groups into organic skeletons is a key research topic in synthetic chemistry given their significant potential to boost biological activity. Despite recent developments of strategies for incorporating trifluoroacetyl moiety via trifluoroacetyl radical intermediates, the practical utilization of inexpensive and readily available trifluoroacetic acids as trifluoroacetyl radical sources has not yet been developed. Herein, an electrochemical strategy has been employed to achieve the radical deoxygenative transformation of trifluoroacetic acids directly with the assistance of PPh₃. The obtained trifluoroacetyl radicals are then coupled with sulfoximine species, thus enabling the synthesis of N-trifluoroacetylated sulfoximines. Additionally, other fluorinated alkyl carboxylic acids, including perfluoro-, difluoro-, and trifluoromethylcarboxylic acids, can also be efficiently utilized under these conditions, leading to their corresponding acylated sulfoximines. Moreover, the trifluoroacetylation of drug-based molecules and the easy execution of scale-up experiments highlight the applicability of this protocol.

Conjugate addition reactions are among the most important transformations in organic synthesis. Electron matching requirements normally restrict the site-selective β-addition of nucleophiles to conjugate acceptors, while regio-reversed α-additions have remained largely elusive. Here we describe a photoinduced polarity transduction strategy that overcomes electronic and steric limitations and enables the exclusively umpolung α-addition of diverse nitrogen nucleophiles to electron-deficient and -neutral alkenes under mild and base-free conditions. This reaction has broad functional group compatibility, shows excellent regioselectivity, and enables late-stage skeletal modification, promising considerable synthetic value. Experimental studies point to a photoinduced through-bond intramolecular charge-transfer (ICT) pathway.

This study describes an efficacious and generally applicable synthetic strategy for the incorporation of biologically and physiologically prominent difluoromethyl entity into synthetically crucial hydrazone scaffolds with bench-stable and easily accessible difluoromethyltriphenylphosphonium bromide. The broad substrate scope, excellent functional group compatibility, feasibility of step and atom economical one-pot synthetic manipulation, and environmentally benign and mild reaction conditions rendered this methodology an efficient tool for the preparation of synthetically and pharmaceutically prominent fluorine-containing imino compounds.

Herein we first report a nickel-catalyzed asymmetric iterative 1,2-reduction of trisubstituted enones to cycloalkanols with two contiguous stereocenters in high yields with excellent diastereo- and enantioselectivities (36 examples, up to 98.5:1.5 er, >20:1 dr, TON = 500). The combined experimental and computational mechanistic studies suggested energy changes during two consecutive reduction processes and provided a range of unique mechanistic rationales that have not been disclosed in nickel-catalyzed asymmetric hydrogenation-related studies.

Enantioselective amine-catalyzed conjugate additions of aldehydes to oxetane- and azetidine-containing nitroolefins afford γ-nitroaldehydes as key building blocks en route to spirocyclic oxetane/azetidine-pyrrolidines. The study provided insights into the stability and reactivity of these β,β-disubstituted nitroolefins and enabled the enantioselective synthesis of chiral oxetanes and azetidines in moderate-to-high yields and enantioselectivities. This approach expands synthetic access to medicinally relevant scaffolds and broadens the scope of enantioselective organocatalytic transformations.

An expedient synthesis of cyclopropane β-amino acid derivatives is reported from readily accessible cyclopropanone surrogates. The addition of stabilized phosphorus ylides to 1-sulfonylcyclopropanols leads to the formation of highly electrophilic alkylidenecyclopropanes shown to be reactive in a telescopic aza-Michael reaction, in mild conditions. The transformation proceeds with complete diastereocontrol in favor of the trans products and is amenable to the rapid production of highly enantioenriched β-amino acid derivatives, peptidomimetics and spirocyclic analogues.

Accessing PAHs having all zigzag edges remains elusive, and this work demonstrates a general synthetic strategy for the construction of one such scaffold, namely, anthanthrene, through Ru(II)-catalyzed APEX reaction at the masked-bay region. The protocol efficiently delivers a range of uniquely substituted anthanthrenes with excellent regioselectivity, which is supported by DFT studies. The synthesis of anthanthrone derivatives, a core structure of vat orange dyes, is another highlight of this study.

Herein we report a diastereoselective synthesis of boryl-substituted vinylcyclopropanes, a class of highly valuable synthetic building blocks, via deborylative cyclization of geminal diboron compounds. The method exhibits broad functional group tolerance and accommodates diverse alkyl and aryl α-substituents. The diastereoselectivity is primarily governed by the α-substituent (alkyl vs aryl), while olefin geometry in the side chain has a secondary influence. Mechanistic studies indicated distinct pathways: a concerted process for alkyl substrates and a carbanion intermediate for aryl derivatives. Synthetic utility of the products was also demonstrated.

A palladium-catalyzed cascade coupling between glycals and racemic α-nitroesters enables the stereoselective construction of C-glycosyl amino acids bearing two contiguous stereocenters, achieving dual stereocontrol (exclusive β-C1, up to 10:1 diastereomeric ratio at C7). This one-pot protocol at room temperature accommodates diverse substrates (25 examples). Mechanistic studies demonstrate that decarboxylation-induced C4-oxyanion directs 1,4-syn selectivity, while steric modulation governs C7 stereochemistry. Synthetic versatility is evidenced by gram-scale synthesis and late-stage functionalization to trihydroxy C-glycosides, 2,3-dideoxy sugars, and 4-O-amino acid conjugates.

A visible light-enabled three-component cascade assembles pyrrolopyrazoles from arylalkynes, benzoquinones, and 5-aminopyrazole through a mechanistically validated carbonyl–alkyne metathesis/(3 + 2)-cycloaddition/1,2-aryl migration sequence. This protocol delivers pyrrolopyrazole heterocycles in up to 96% yield with excellent functional group tolerance. Preliminary biological screening identified promising antitumor activity in selected products, highlighting the potential value of this method. The proposed reaction mechanism is supported by control experiments.

A palladium-catalyzed [3 + 2] cycloaddition of cyclopropenones with N-allenamides has been developed. This methodology facilitates the synthesis of γ-amino-α′-methylenecyclopentenones in moderate to excellent yields with good regioselectivity and compatibility with various functional groups. The employment of N-allenamides as versatile 2C synthons enables simultaneous incorporation of both a nitrogen atom and a methylene group into cyclopentenones. Furthermore, this approach exhibits reverse regioselectivity when compared to general allenes. Density functional theory calculations successfully elucidated the origin of the observed regioselectivity.

We report an ether-directed enantioselective C(sp²)–H borylation catalyzed by a chiral bidentate boryl ligand (CBL)/iridium system for constructing axially chiral biaryls. This method delivered diverse chiral biaryls with good to high enantioselectivities, accommodating varied electronic and steric substituents on the aryl rings. Gram-scale synthesis and downstream transformations of the C–B bond underscored its practicality.

Herein, we report a generally applicable hydrogen-bond-mediated glycosylation protocol of glycosyl picolinate donors with a charged (thio)urea hydrogen-bond-donor catalyst. A variety of nucleophiles, including complex natural products, glycosides, amino acids, and less nucleophilic phenolic acceptors were also glycosylated successfully. Hydrogen-bond-mediated glycosylation systems combined with different strategies were also explored to achieve stereoselective glycosylation. A mechanistic study revealed that catalysts form the donor-catalyst noncovalent complex through hydrogen bonds and then produce the oxocarbenium species.

Herein, we report an aerobic palladium-catalyzed aza-Wacker cyclization to produce spirocyclopentene-3,2′-indolines with vicinal stereocenters. Using 1,2-bis(diphenylphosphino)benzene (dppbz) and pyridine as ligands, we achieved a ligand-modulated diastereodivergent synthesis, producing cis- and trans-spirocyclopentene-3,2′-indolines with exceptional yields and diastereoselectivities. Density functional theory (DFT) calculations revealed that selective aza-Wacker cyclization proceeds through distinct trans- and cis-aminopalladation mechanisms.

Chiral phospholane ligands and catalysts have been widely applied in asymmetric catalysis and synthesis. However, the construction of the chiral phospholane skeleton remains challenging and primarily relies on the use of chiral auxiliaries or resolution. In this work, a highly enantioselective and diastereoselective synthesis of P-stereogenic phospholane oxides has been achieved through a cobalt-catalyzed desymmetric hydroalkylation strategy. This method enables the construction of two discrete stereocenters with excellent yields and enantiomeric excesses.

An EnT-mediated C3-N-heteroarylation of 2-aryl quinoxalines via decarboxylative radical–radical cross-coupling (C(sp²)–C(sp²)) with oxime esters is presented. Upon photoactivation, the triplet energy of the photocatalyst is transferred to both reacting partners (oxime ester and 2-phenylquinoxaline). The excited oxime ester undergoes decarboxylative fragmentation to a C-centered N-heteroaryl radical and an N-centered imine radical. The former attacks the C3 site of the quinoxaline diradical, while the latter acts as a hydrogen atom abstractor (HAA). Computational studies revealed that C–C bond formation with the heteroaryl radical is energetically more favorable than C–N bond formation.

The Nef reaction for conversion of nitro compounds to aldehydes is described. Various functional groups, such as ethers, silyl ethers, acetals or esters, were tolerated to give aldehydes in high yields using Cs₂CO₃ and singlet oxygen as an oxidant. Transformations of nitromethyl groups into hydroxymethyl groups were achieved in a one-pot operation. The mechanism involved in the Nef reaction was studied using ion chromatography and radical scavengers, which resulted in the proposal of two unique reaction pathways.

We report here a cascade process integrating the hexadehydro Diels–Alder (HDDA) reaction with alkynyliodanation, enabling efficient synthesis of highly substituted aryl-λ³-iodanes. Heating a mixture of a tetrayne and an alkynylbenziodoxole induces regioselective insertion of the tetrayne-derived aryne into the alkynyl–iodine(III) bond, yielding a 1,4-dialkynyl-2-iodanyl-3-aryl(or alkyl)benzene derivative. The unique regiochemistry facilitates subsequent π-extension, allowing divergent access to polyaromatic frameworks, such as helicenes and cyclopenta[cd]pyrenes, underscoring the utility of aryne carboiodanation in complex aromatic synthesis.

Reductive hydroamination of stable and readily available nitroarenes with unsaturated hydrocarbons represents practical access to amines. Herein, we report a simple Cu-catalyzed amine synthesis via the reductive hydroamination of nitroarenes with inactive diarylacetylenes. A series of diarylacetylenes are successfully transformed into secondary amines under mild conditions with good functional group tolerance.

The bromination of cubane 1,4-diester is described for the first time. The versatility of the C–Br bond for forging C–S and C–C bonds was demonstrated. The fluorosulfonylation reaction allowed the first entry of the cubane in click chemistry illustrated with nucleophiles, electrophiles, and alkynes. The grafting of appendages was illustrated with amino acids and dipeptides, enabling the discrimination of the diesters via cyclization into “fused cubane-lactam” structures.

A Pd(II)-catalyzed cascade annulation of 4-hydroxy-3-maleimidecoumarin with alkynes has been demonstrated. This unique strategy highlights an interesting process for the cascade formation of three rings (three-, five-, and six-membered) of carbocycles and heterocycles through spiro-annulation followed by cyclization. This strategy offers an attractive platform for synthesizing various coumarin-fused complex structures in good yields. Additionally, six synthesized compounds have been unambiguously confirmed by single-crystal X-ray diffraction analysis.

Herein, we report a sodium tert-butoxide-promoted reduction of N-heteroarenes using ammonia borane and dimethyl sulfoxide (DMSO) under mild reaction conditions. This method demonstrates broad functional group compatibility across diverse N-heteroarene substrates. Notably, substituting DMSO with deuterated DMSO-d₆ enables the synthesis of C3-deuterated 1,2,3,4-tetrahydroquinolines with remarkable positional selectivity. Mechanistic investigations indicate that the protons are derived from both ammonia borane and DMSO. This strategy establishes a novel and environmentally benign approach for the synthesis of (deuterated) N-heterocycles, offering practical advantages in terms of operational simplicity and sustainable reaction conditions.

Lauicyclone A (1), a new skeletal diterpenoid characterized by an unprecedented carbon skeleton, represents the first reported natural product featuring a complex tricyclo[4.3.1]decane framework. Along with Lauicyclones B–E (2–5), all five compounds were isolated from Croton laui. Comprehensive spectroscopic analyses, quantum-chemical calculations, and X-ray diffractions were used to identify their structures. The antitumor mechanism of compound 1 was investigated using ¹H NMR-based metabolomics.

Herein, we report the asymmetric synthesis of 10-demethoxyvincorine in 12 steps. The synthesis is highlighted by several key transformations: (1) a Pd-catalyzed Catellani-type reaction for the preparation of C2-alkylated tryptamine, (2) a chiral phosphoric acid (CPA)-catalyzed asymmetric bromocyclization to construct enantioenriched 3a-bromo-hexahydropyrroloindoline, (3) a dual Ni/Ti-catalyzed reductive cyclization to establish the bridged ring system, and (4) a SmI₂-promoted reductive cyclization to forge the strained E-ring.

The cross-electrophile coupling of organobromides is widely utilized in organic synthesis but generally requires undesirable amide solvents (e.g., DMF, DMA, and NMP). We report that the combination of a strongly donating, bidentate nitrogen ligand, LiI, and 4-picoline enables coupling in a variety of alcohol, ester, and ethereal solvents at up to 50 g scale. An improved synthesis of the optimal ligand, 4,4′-bis(dimethylamino)-2,2′-bipyridine, is also reported on the basis of the reductive homocoupling of 4-dimethylamino-2-chloropyridine.

DNA-encoded library (DEL) technology is a transformative tool for identifying bioactive compounds in pharmaceutical research. This study presents an optimized copper-mediated reaction to synthesize N-sulfonylamidine derivatives from DNA-conjugated alkynes and sulfonyl azides under mild conditions. Amines serve as nucleophiles, enabling selective functionalization under mild conditions while preserving DNA integrity. Through systematic refinement of reaction conditions and substrate evaluation, the approach demonstrated a high tolerance to diverse functional groups, significantly expanding DEL-accessible chemical space. The developed DNA-compatible method underscores the role of DELs in enhancing drug discovery by facilitating the introduction of novel pharmacophores into compound libraries.

This report describes a new kinetic resolution–asymmetric reductive amination strategy to collectively gain access to both primary and secondary chiral NH-unprotected amines. Catalyzed by the complex of iridium and bulky and tunable phosphoramidite ligands, various ketones and racemic primary amines could be smoothly converted to two different types of amine products. Bronsted acids as additives play triple roles, decreasing the inhibitory effect, promoting the formation of the imine intermediates, and guiding the reaction to proceed through “outer-sphere” H-addition along with the bulky ligand.

In this study, we developed a photoredox-catalyzed defluorinative cross-coupling method for trifluoroketones and alkyl boronic acids. The reaction afforded a series of novel α,α-difluoroketone derivatives, and in vitro fungicidal activity revealed that some of these compounds exhibited moderate to excellent activity against Rhizoctonia solani and Botrytis cinerea. In particular, compound 3d showed an EC₅₀ value of 4.27 μg/mL against B. cinerea and can be used as a fungicidal lead compound for further optimization.

Six quinoidal compounds terminated by oxindole have been synthesized via selective nucleophilic addition, dehydroxylation, and oxidation. Through the modification of the quinoidal core and terminal benzene rings with fluoride atoms or cyano groups, the LUMO energy levels of the quinoidal compounds can be tuned within the range −4.05 to −4.54 eV. The quinoidal molecules exhibited electron transport behavior and can be used as dopants to dope an oligo(ethylene glycol)-substituted polythiophene.

By leveraging the Rh-catalyzed asymmetric skeletal editing of 1,2,3-thiadiazoles, we successfully achieve the ligand-controlled enantioselective and regiodivergent synthesis of structurally diverse 2- and 3-alkylidene 2,3-dihydrothiophenes. Late-stage structural editing of complex natural and drug molecules is also enabled.

A series of bisphosphine-grafted amphiphilic polymers based on polyethylene glycol-poly(vinylethylene glycol) (PEG–PVEG) copolymers have been synthesized by using allylic etherification polymerization as a pivotal step. Self-assembling of the palladium complexes of the obtained amphiphilic polymers into spherical micelles has been investigated by UV–vis, DLS and TEM analysis. The outstanding catalytic performance of the present micellar palladium catalyst has been evidenced in the aqueous Suzuki–Miyaura coupling reaction, achieving remarkable efficiency even at a low catalyst loading of 100 ppm within 2 h.

Stereoisomerism in pillararenes, particularly chiral isomerism from atropisomers, has intrigued organic chemists. Herein, we report the synthesis and characterization of a trimacrocyclic system formed by fusing two [8]cycloparaphenylenes with a pillar[6]arene. This system exhibits unique stereoisomerism, yielding a racemic mixture and a meso compound. The isomers were characterized using NMR, HRMS, and single crystal X-ray diffraction. This study offers valuable insights into constructing chiral isomers in macrocycles and enriches our understanding of stereochemistry.

Replacing alkyl organometallic reagents with alkyl bromides to achieve desulfurative alkylation of thioethers has been a long-standing challenge in desulfurative functionalization of organosulfur compounds. Herein, we report a copper-catalyzed reductive tertiary alkylation of β-acyl allylic sulfides with α-carbonyl alkyl bromides under mild reaction conditions. The reaction accommodates a broad substrate scope with good functional group compatibility, providing a direct route to install diversified (sp³)-carbon quaternary centers at the allylic position of α-branched enones. Further synthetic applications of this protocol have been demonstrated with scale-up experiments and late-stage modification of the products.

Syntheses of guanidino alkaloids (+)- and (−)-batzelladine C are described. The key feature of the syntheses is the cyclization/carbonylation/double cyclization cascade of optically active propargyl guanidine. The tricyclic guanidino cores bearing three stereogenic centers and an ester functionality were constructed in a single step. The esters with a hydroxy group were then converted into (+)- and (−)-batzelladine C. The absolute configuration of natural (−)-batzelladine C was revised to the (11S,13R,15S) configuration.

We have developed a novel photocatalytic system using readily available triarylmethyl cations for radical-mediated (4 + 2) and (2 + 2) cycloaddition reactions. A variety of substituted triarylmethyl cations were investigated, and the optimal catalyst exhibited high efficiency and broad substrate scope, affording the desired cycloadducts in good to excellent yields with high regio- and diastereoselectivities. Furthermore, the catalyst could be immobilized on a polymer support and reused multiple times without a significant loss of activity.

A copper-catalyzed asymmetric cross 1,3-dipolar cycloaddition between 2-aminoallyl zwitterions generated in situ from ethynyl methylene cyclic carbamates and N,N′-cyclic azomethine imines has been realized. The reaction, which utilizes a commercially available chiral tridentate N-ligand, delivers a range of functionally rich chiral hexahydro-8H-pyrazolo[1,2-a][1,2,4]triazin-8-one derivatives in 51–99% yields with good to high enantioselectivities (44–95% ee).

gem-Difluorinated carbocyclic rings are attractive motifs in drug development. Herein, we report the transition-metal free cascade reaction of bicyclo[1.1.0]butanes (BCBs) with gem-difluorocyclopropenes for the synthesis of gem-difluorinated carbocyclic rings with excellent regio- and diastereoselectivity. This method was successfully applied to provide a broad range of gem-difluorinated cyclopentenes and cyclopropanes, which could undergo a variety of difluoromethylene (CF₂) retaining transformations.

Perakine reductase (PR) is an aldo-keto reductase (AKR) carbonyl reductase. His126 is one of the AKR catalytic tetrads in PR. Substitution of His126 with any other amino acids except Gln switched PR to an ene reductase. Molecular simulation suggested that the substrate-binding pose and the properties of the 126 residue determined the chemoselectivity. Given the strict conservation of His126 in AKR superfamily carbonyl reductases, modification of the corresponding site is a feasible strategy to design AKR-derived novel ene reductases.

A palladium-catalyzed reaction of indoles with cyanoacetate salts enables the synthesis of 2,6-disubstituted indolines via tandem dearomatization/decarboxylative cyanomethylation. Remarkably, this is the first example of indole difunctionalization at the C2 and C6 positions. Moreover, this methodology extends to the palladium-catalyzed cyclization/decarboxylative cyanomethylation of aryl halide-tethered alkenes.

Herein, we developed a new method for the synthesis of aryl-substituted allenes through a nickel-catalyzed reductive coupling reaction between secondary propargyl carbonates and aryl halides. By employing the dimethyl-1,10-phenanthroline ligand, we achieved a ligand-controlled, regioselective nickel-catalyzed reductive arylation, overcoming the structural limitations of propargyl electrophiles. Notably, this reaction exhibits exceptional functional group compatibility, rendering it particularly suitable for late-stage allenylation modifications of complex molecules.

A new class of chiral spiro monophosphinites, based on a unique non-C2-symmetric 3-oxo-1,1′-spirobiindane scaffold featuring a large dihedral angle, has been effectively designed and synthesized. From readily accessible resources, these chiral spiro monophosphinites were synthesized via eight steps in 16–32% yields. Their excellent performance in the rhodium-catalyzed asymmetric hydrogenation of β-dehydroamino acid esters underscores the critical impact of the large dihedral angle in enhancing the activity and enantioselectivity.

Due to the unique electronic structure, azulene-containing polycyclic aromatic hydrocarbons attract significant attention toward tuning the chemical and electronic properties of benzenoid carbocyclic systems. Here, we report the synthesis and properties of two types of azulene fused, seco-hexabenzocoronene-based nanographenes. The X-ray crystallographic analysis indicated their nonplanar structures with highly torsional periphery in the solid structures. The typical narrow highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) energy gaps, long-wavelength absorption, and anti-Kasha emissions were investigated by experimental and computational studies. Interestingly, these nanographenes exhibited a pronounced photothermal effect.