We report a synergistic dual-catalytic approach that combines a commercially available chiral -heterocyclic carbene (NHC) with a simple achiral thiourea catalyst to achieve a dearomative Michael addition. This cooperative system enables noncovalent activation modes that promote efficient access to dearomatized 2,3-dihydrobenzofuryl and fluorinated oxindole frameworks. The methodology proceeds in good yields and delivers products with excellent stereocontrol (dr of >20:1 and ee up to >99%). This strategy not only provides a general platform for the synthesis of densely functionalized oxindoles but also highlights the power of synergistic organocatalysis in addressing challenging fluorine-incorporated stereogenic motifs.

Herein, we present a highly efficient (one-pot) and unprecedented method for synthesizing 1,4-Benzoxazinones and 4,1-Benzoxazepinones under transition metal-free conditions through direct aryl C-H amination. For the first time, this work harnesses the 1,3-bis-electrophilic potential of α-bromohydroxamates, enabling direct O-alkylation of phenols and benzyl alcohols via an in situ-generated aza-oxyallyl cation, followed by aryl C-H amination via a nitrenium ion catalyzed by hypervalent iodine. When p-OMe-substituted phenols are used, the current system produces spiroxazolidinones, a class with limited, radical-based methods reported in the literature. Late-stage modifications of natural products and other valuable synthetic transformations underscore the synthetic utility of the method.

A geometry-dependent intramolecular MHAT (metal-hydride hydrogen atom transfer) cyclization of olefins using carbethoxy methylene isoindolone as a radical acceptor has been developed for the synthesis of pyrroloisoindolone and pyridoisoindolone derivatives. The regioselectivity is dictated by the geometry of the substrate. While -carbethoxy methylene isoindolones undergo selective 6 HAT cyclization to afford pyrido[2,1-]isoindolones, the corresponding -isomers favor 5 cyclization, producing pyrrolo[2,1-]isoindolones. The mechanistic understanding was further substantiated by control experiments.

Lasso peptides and lanthipeptides are two major classes of ribosomally synthesized and post-translationally modified peptides (RiPPs), each defined by distinct post-translational modification (PTM) enzymes. We identify a hybrid biosynthetic gene cluster that integrates PTM enzymes from both pathways to produce a unique lasso peptide featuring a dehydroalanine residue and C-terminal Asp side-chain methylation. Elucidation of its biosynthesis uncovers unprecedented combinatorial RiPP maturation. This study establishes a paradigm for hybrid RiPP biosynthesis and enables discovery and engineering of novel RiPPs.

Employing a sequential gold and organocatalytic system, we have achieved a one-pot double annulation of versatile 1,3-dicarbonyl compounds bearing a 3-butynoic acid moiety. This process proceeds through a gold-catalyzed cyclization, followed by a thiourea-catalyzed intramolecular vinylogous aldol reaction. By strategically employing desymmetrization and dynamic kinetic resolution, respectively, this methodology enables the efficient and asymmetric construction of a series of spiro-butenolide architectures incorporating contiguous tetrasubstituted carbon stereocenters.

Through the strategic integration of 3,4-dinitropyrazole with trinitromethyltriazole and oxadiazolone units, two novel asymmetric bicyclic energetic materials, 5-(3,4-dinitro-1-pyrazol-5-yl)-3-(trinitromethyl)-1-1,2,4-triazole () and 3-(3,4-dinitro-1-pyrazol-5-yl)-1,2,4-oxadiazol-5(4)-one (), were successfully designed and synthesized. Systematic testing revealed that the nitro-functionalized extended conjugated structure achieves excellent detonation performance ( = 9273 and 8485 m·s, = 39.4 and 31.3 GPa) while maintaining moderate thermal stability ( = 150.7 and 198.5 °C) and mechanical sensitivity (IS = 8.9 and 12 J, FS = 168 and 240 N). Furthermore, exhibits a suitable melting point ( = 82.2 °C) and decomposition temperature, demonstrating its potential as a candidate for melt-cast explosive applications.

A photocatalyzed radical decarboxylative hydroalkylation of alkynes and alkenes has been developed for the efficient synthesis of allylamine and arylpropylamine derivatives. This protocol employs organic 4CzIPN as a photocatalyst and avoids the use of transition metals, featuring simple and mild conditions. The mechanistic study suggested that the reaction was preceded by the decarboxylation of amino acids to give alkyl radicals, followed by radical addition to a carbon-carbon triple bond or double bond. A range of arylpropylamines were prepared with up to 88% yields, and allylamines were synthesized with good -selectivities. This process represents an important approach for the high-value-added transformation of unsaturated hydrocarbons under simple and mild conditions.

-Annulated indenofluorene (), a structural isomer of the well-known -annulated perylene (), has been synthesized. While the band gap of is larger than that of perylene, the band gap of (1.40 eV) is smaller than that of parent indeno[2,1-]fluorene (1.60 eV) due to the inclusion of a nearly planar 8π azepine ring in the π-conjugated backbone, enhancing the core antiaromaticity. The ground state properties are evaluated by structural (single-crystal) and spectral (NMR, UV-vis-NIR, and CV) analyses and supported by computations (NICS and ring current). is an ambipolar material with good electron mobility (1.58 × 10 cm V s) and high hole mobility (1.79 × 10 cm V s), surpassing the hole mobility of the unipolar isomer.

Norsecurinamine B represents the first example of an NH-bridged dimeric alkaloid, in which two norsecurinine monomers are joined through an amine linker at their faces. However, the face of norsecurinine is intrinsically favored for nucleophilic attack, rendering the synthesis of the target challenging. Herein, we disclose a convergent total synthesis of norsecurinamine B, highlighting the strategic design elements that effectively address this stereochemical challenge.

Chlocarbazomycins are bioactive carbazoles with therapeutic potential. Here, we report a conserved gene cluster () that directs its biosynthesis via a novel pathway. This cluster encodes a versatile tailoring system, including a regioselective halogenase (CczH), dedicated hydroxylases (CczA/J/D), and a bifunctional methyltransferase (CczI) that iteratively methylates and accelerates N-OH dehydroxylation. Our findings provide new enzymes for carbazole pathway engineering and structural diversification.

Monosubstituted alkenes are widely utilized in organic synthesis. Although remarkable progress has been made in chelation-assisted alkenyl C-H functionalization, monosubstituted aliphatic alkene remains a challenging target due to reactivity and selectivity issues. Herein, we report on the first sequential α/β-C-H functionalization of monosubstituted aliphatic alkenes derived from bishomoallyl amines. This protocol showed wide functionality tolerance and afforded C-H alkenylation and allylation as well as alkynylation products with excellent regio- and stereoselectivity.

Electrochemistry offers new opportunities for radical Truce-Smiles rearrangement (TSR). Herein, we disclose an electrochemical decarboxylation of redox-active esters that triggers a nondesulfonylative TSR of -arylsulfonylpropiolamides, delivering 4-aryl-5-alkyl isothiazolidinone dioxides. We uncovered a subtle interplay between anodically generated metallic salts and the selected electrolyte anion, favoring either kinetic or thermodynamic isomers with moderate and high diastereoselectivities, respectively. Further transformation smoothly provides the formal desulfonylative TSR adduct, expanding the synthetic utility of the method.

We report an efficient and highly selective synthesis of azaspiro polycyclic scaffolds with excellent chemo-, regio-, and diastereoselectivities. This method exhibits broad substrate scope (44 examples), and the resulting tetracyclic compounds can be readily elaborated to complex pentacyclic lactams (8 examples). DFT calculations demonstrate thermodynamic control over the diastereoselectivity. Notably, the lead compound exhibiting nanomolar cytotoxicity against PANC-1 cells (IC = 92 nM), underscoring the potential for generating natural product-like antitumor agents.

A TfO-mediated formal [3 + 2]-cycloaddition of phenylarsine oxide and internal alkynes has been developed. An initially formed arsenic dication undergoes disproportionation to form key arsenic cation species, which are then coupled with alkynes, finally delivering the corresponding 2,3-disubstituted benzarsole derivatives with concomitant unique phenyl group migration. This strategy is also applicable to the three-component coupling of phenylarsine oxide, arylboronic acids, and alkynes. Moreover, ring transformations of the obtained benzarsoles are described.

This study underlines the strategic use of privileged scaffold hybridization in designing and synthesizing a unique new class of polynitro energetic compounds. These compounds exhibit high densities (1.77-1.87 g cm), high positive heats of formation (652.9-793.3 kJ mol), good detonation performance (VOD, 8165-8721 m s; DP, 27.38-32.87 GPa), good thermal stability (118-213 °C), and low sensitivity (IS > 7.5 J; FS > 240 N). These findings demonstrate that the fused [5,5,5,6]-tetracyclic backbone in these energetic compounds plays a vital role in achieving excellent energetic performance and stability.

We report a method for the stereospecific construction of sp-sp carbon-carbon bonds using alcohols and carbanion nucleophiles. The process is based on a circular phosphorus(V) manifold which starts and ends with triphenylphosphine oxide. The redox neutral approach eliminates the need for hazardous diazodicarboxylate oxidants and allows for recovery and recycling of triphenylphosphine oxide. Alcohol activation is achieved through formation of alkoxyphosphonium triflates, which are kinetically stable, and undergo coupling with exogenous carbanion nucleophiles. In this manner, a range of alcohols undergo deoxyalkylation with inversion of configuration in moderate to excellent yield.

The transformation of 1,3-enynes is one of the important methods for obtaining a variety of valuable organic molecules. In the past few decades, significant progress has been made in the difunctionalization of 1,3-enynes via a radical process. However, the hydrofunctionalization of 1,3-enynes has been studied less. Herein, we describe the first example of reductive Co-MHAT-catalyzed Wacker-type oxidation of 1,3-enynes under air conditions with Markovnikov regioselectivity. Valuable conjugated ynones were obtained from the readily available starting material. Furthermore, a broad substrate scope with good functional group compatibility, simple operation, mild conditions, diverse downstream transformations, and excellent late-stage modifications demonstrated this method has significant advantages in practical utility.

The alkylation of -sulfinylamines has emerged as a straightforward and promising platform for the construction of sulfinamides. Nevertheless, extant strategies─whether through two-electron nucleophilic addition or single-electron radical pathways─remain confined to two-component reactions, exhibiting intrinsic constraints in terms of carbon nucleophile diversity, synthetic efficiency, and structural variety of the products. Herein, we have successfully developed a photocatalytic radical-polar crossover process that addresses these challenges by enabling a three-component coupling reaction of Tr-NSO, alkenes and alkyl/aryl trifluoroborate salts. Despite the difficulty in controlling chemoselectivity among competing pathways, this strategy affords highly functionalized sulfinamides that are otherwise inaccessible through conventional means. Furthermore, mechanistic investigations, involving the trapping of radical and carbanionic intermediates along with fluorescence quenching studies, offer compelling support for the proposed reaction pathway.

Herein, we report a diazo-controlled Cu(II)-catalyzed annulation of naphthylamines that provides divergent access to benzo[]indole frameworks with excellent selectivity. Different diazocarbonyl compounds govern the reaction pathway, and malonate-derived carbenes promote C-H insertion/annulation, whereas phosphonate analogues undergo N-H insertion followed by cyclization. The transformation exhibits broad substrate scope, high yields, and gram-scale practicality. Detailed control, labeling, and intermediate-isolation studies further establish the mechanistic divergence between these pathways. Several products display bright blue-to-green fluorescence with high quantum yields, underscoring the potential of this Cu-catalyzed platform for the construction of functional benzo[]indole fluorophores.

The stereoselective synthesis of recently discovered lipofuscin fluorophore -A2E, a C3,C4-bis-polyenylpyridinium salt derived from all--retinal, which has been detected in human, pig, mouse, and bovine eyes, has been completed. The Suzuki-Miyaura cross-coupling reaction and Horner-Wadsworth-Emmons condensation were the key synthetic steps for the construction of the tetraenyl and pentaenyl arms, respectively, starting from a properly functionalized pyridine-3,4-dialdehyde surrogate, followed by pyridine alkylation. Subtle changes in the H NMR and C NMR spectra of the synthetic compound and natural compound suggested the structural revision of the latter, for which the C13'═C14' isomer at the longer C3-unsaturated pentaenyl chain of the pyridinium ring was proposed. The synthesis confirmed the alternative stereostructure of the natural pigment, which should be named -A2E, thus correcting the double bond geometry of the natural fluorophore at C13'═C14'.

A serendipitous outcome in the mandelic acid-mediated imine condensation of a tetraphenylethene-derived tetraaldehyde and tris(2-aminoethyl)amine led to [2 + 4] face-rotating molecular boxes, rather than the expected [6 + 8] cubic cages. The resulting -symmetric assemblies feature two homochiral tetraphenylethene facial units and four unreacted amine handles. Mandelic acid engages in cooperative hydrogen bonding, steric effect and C-H···π interactions that steer the assembly pathway and supramolecular chirality. NMR, ECD, and X-ray analyses confirm the formation of a pair of diastereomeric supramolecular complexes exhibiting distinct optical activity in solution.