Catalytic reduction of unsaturated substrates provides a powerful tool for bulk and fine chemical synthesis. However, very few examples have been reported on the reductive transformation of thioamides, presumably because of the poisoning of catalysts by sulfur-containing molecules. Herein, we describe an efficient and sustainable hydrogenative coupling of thioamides with olefins under electrocatalytic conditions. The key to success for this reductive process is the application of an earth-abundant cobalt complex as the cost-effective and robust molecular electrocatalyst. As only protons (H⁺) and electrons (e^–) as the hydrogen source and redox equivalent, this polarity-reversed electrochemical protocol is showcased by highly selective and straightforward synthesis of a wide range of α-branched amines, as well as deuterium isotope labeling applications. Over 60 α-branched amines, including 12 deuterated analogues, have been successfully synthesized. Notably, a variety of functional groups, including aryl halides, esters, and nitriles, are well tolerated under the mild electrochemical conditions. Furthermore, late-stage modification of complex molecules has also been achieved. Mechanistic studies indicate that the in-situ generated imines and α-amino radicals by cobalt-electrocatalytic desulfurization of thioamides are identified as the key intermediates in this transformation. This work provides an alternative and versatile method for the synthesis of structurally diverse α-branched amines, with advantages including sustainability, high selectivity, and compatibility with isotope labeling and complex molecular functionalization.

α-Hydroxy-β-amino ketones are key structural motifs in many bioactive compounds, yet their asymmetric synthesis remains challenging. Although numerous approaches for accessing simple amino alcohols are well established, methods specifically targeting the construction of the α-hydroxy-β-amino ketones motif have been rarely explored. Herein, we report a green biocatalytic approach to access these scaffolds via cross-benzoin condensation of α-amino aldehydes and aryl aldehydes using an engineered ThDP-dependent enzyme. Through protein engineering of benzaldehyde lyase from Pseudomonas fluorescens (PfBAL), the variant A28G was identified that efficiently catalyzes this transformation. Compared with the wild-type enzyme, which gave only 33% yield of the desired product along with 49% self-benzoin byproduct, the A28G mutant significantly improved the cross-coupling efficiency while reducing the homocoupling side reaction to just 3%. Under optimized aqueous conditions, the PfBAL A28G catalyst accommodated a broad range of aryl aldehydes bearing electron-withdrawing or electron-donating substituents, as well as heteroaromatic (furan, thiophene) and disubstituted derivatives, delivering the corresponding α-hydroxy-β-amino ketones in up to 98% isolated yields with excellent enantioselectivities (up to >99% ee). The practical utility of this method was demonstrated by gram-scale synthesis (1.13 g of product 3a) with 81% yield and retaining 96% ee. Molecular dynamics simulations revealed that the A28G mutation shortens the attack distance between the Breslow intermediate and the α-amino aldehyde acceptor from 6.4 Å to 4.5 Å, accounting for the enhanced reactivity. Moreover, differential binding of the product enantiomers to the active site explains the strict R-configuration control. This work not only provides a green, atom-economic, and highly stereoselective route to enantioenriched α-hydroxy-β-amino ketones under mild aqueous conditions but also expands the synthetic repertoire of ThDP-dependent enzymes to nitrogen-functionalized aldehyde acceptors, opening new avenues for biocatalytic C–C bond formation in pharmaceutical chemistry and natural product synthesis.

This work presents the first practical and modular strategy for visible-light-induced, site-selective C(sp²/sp³)-H functionalization of inert C–H bonds in feedstock chemicals. Utilizing tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer photocatalyst, a broad range of substrates, including ethers, thioethers, amides, alkanes, aldehydes, and complex bio-related molecules, undergo efficient epoxidation with allylic peroxides under mild, oxidant-free, and operationally simple conditions. The protocol affords diverse, highly functionalized oxiranes with excellent site-selectivity and wide functional group tolerance at room temperature under 390 nm light irradiation. Its synthetic utility is further demonstrated by gram-scale synthesis and versatile post-transformations, such as ring-opening, reduction, halogenation, azidation, and one-pot cyclizations. Molecular docking studies reveal that the resulting epoxides exhibit favorable binding interactions with kinase proteins, highlighting potential applications in biochemical research and drug development. This visible-light-mediated C–H epoxidation offers a green, efficient, and modular route to high-value oxiranes, expanding the toolkit for organic synthesis and medicinal chemistry.

The carbazolyl phosphonic acid-based self-assembled molecules (SAMs) are a promising candidate as hole transport layers (HTLs) for organic solar cells (OSCs). However, the SAM films tend to have incomplete surface coverage on the electrode, such that interfacial defects adversely affecting device performance and reproducibility. To address this issue, we design three asymmetric SAMs (4PACz-1N, 4PACz-2N, and 4PACz-3N) featuring isomerized naphthyl-carbazole skeletons. Skeleton isomerization simultaneously regulates dipole properties to elevate the work function of ITO anodes and minimizes energy barriers for hole extraction. Meanwhile, the conjugation skeleton expansion can further promote molecular stacking and reduce surface energy, leading to more complete coverage on the ITO and more intimate contact with the active layer, thereby enhancing the reproducibility of the device. Consequently, these isomerized SAMs demonstrate synergistic improvements in charge extraction efficiency, device reproducibility, and interfacial stability. These features significantly improve charge dynamics and interfacial stability, and demonstrate universal applicability in numerous systems. Notably, binary devices based on 4PACz-1N can achieve an excellent efficiency of 20.27% with outstanding device stability. This work highlights the significance of the skeleton isomerization strategy for developing highly efficient HTL.

Chiral 3-hydroxy-3-substituted oxindoles represent privileged heterocyclic cores ubiquitous in pharmaceuticals, lead compounds, and bioactive natural products. Despite the establishment of numerous synthetic methodologies for the asymmetric construction of 3-hydroxy-3-substituted oxindoles, the enantioselective construction of such frameworks bearing multiple stereogenic centers under mild conditions remains challenging. Most existing approaches require transition-metal catalysts, harsh reaction conditions, or prefunctionalized starting materials, which limit their practical utility. In recent years, N-heterocyclic carbenes (NHCs) have emerged as powerful and efficient organic catalysts in an expanding range of asymmetric transformations. Many novel activation modes, including the generation of acyl azoliums and enolates, have been developed using NHCs as key organocatalysts. Consequently, diverse functional and biologically active molecules have been constructed via NHC-catalyzed reactions. Among these intermediates, enolate intermediates play a pivotal role in NHC catalysis and are widely utilized as two-carbon (2C) synthons in [2 + 4] cycloadditions to construct heterocyclic compounds. However, exploiting alternative [2 + n] annulation modes, particularly [2 + 2] cycloadditions, remains of considerable scientific interest and practical relevance due to the potential for generating strained β-lactone intermediates that can be further elaborated. Herein, we report an NHC-catalyzed enantio- and diastereoselective [2 + 2] cycloaddition/ring-opening sequence that provides quick and efficient access to structurally diverse 3-substituted-3-hydroxyoxindoles bearing two chiral centers. The reaction tolerates a broad scope of substrates, affording the products in generally moderate to excellent yields with good optical purities. Moreover, the reaction is scalable to a 10-fold loading, delivering the target product in 84% isolated yield with 96 : 4 er and >20 : 1 dr. Notably, the obtained products can undergo diverse further derivatizations without erosion of stereoselectivity, underscoring their utility as chiral building blocks. We proposed a plausible reaction mechanism involving the formation of an NHC-bound enolate followed by a stereoselective [2 + 2] cycloaddition to generate a spirocyclic β-lactone intermediate, which then undergoes ring opening. Key intermediates were detected by HRMS and NMR, providing solid evidence for the proposed pathway.

Glycans that are widely distributed in nature possess diverse biological activities. However, the inherent structural microheterogeneity of natural glycans impedes their functional evaluation. Chemical glycosylation serves as a powerful approach to access well-defined complex glycans for structure-activity relationship studies. In particular, one-pot multistep glycosylation enables the efficient assembly of complex glycans by eliminating intermediate purification and minimizing protecting-group manipulations. Nevertheless, a key limitation of this traditional approach is its inefficient late-stage coupling, which might result in the loss of valuable advanced donors. Here, we developed a photolabile ester-mediated one-pot glycosylation–deprotection–glycosylation strategy for the rapid assembly of both linear and branched oligosaccharides. Based on the photolabile ortho-nitro-benzyloxycarbonyl (oNBC) ester-mediated one-pot strategy from the reducing end to non-reducing end, efficient and stereoselective synthesis of oligomannoside, oligofucoside, and five types of HBGAs including A_tri, B_tri, H1, H3 and Le^b antigens was achieved. Various glycosyl leaving groups including ynenoates, trichloroacetimidates, N-phenyl trifluoroacetimidates, and thioglycosides were successfully employed in these photo-mediated one-pot reactions, with solvent and temperature identified as critical factors for stereoselective glycosidic bond formation. In contrast to the photolabile o-nitrobenzyl (oNB) group, the photolabile oNBC group could be readily introduced on the primary and secondary hydroxyls of sugar building blocks under mild basic conditions, which were fully compatible with common ester protecting groups. When installed at the C-2 position of glycosyl donors, the oNBC group typically favored the formation of β-glycosidic bonds. The binding results indicated that the H1 receptor exhibited superior binding to norovirus-like particles relative to the H3 receptor, thereby serving as a valuable tool for assessing norovirus vaccine-elicited antibodies. The photolabile ester-mediated one-pot strategy provides a versatile platform for the streamlined assembly of architecturally complex and branched glycans.

The incorporation of fluorophores into vinyl polymer backbones is highly desirable for developing advanced functional materials, yet remains a significant challenge due to the inert nature of the all-carbon backbone. In this work, we present a versatile strategy to overcome this architectural limitation by directly integrating fluorophores into the vinyl polymer backbones. This is accomplished through the design and efficient synthesis of a novel macrocyclic monomer that incorporates tetraphenylethene (TPE), a well-known aggregation-induced emission (AIE) luminogen. Using photoinduced electron transfer–reversible addition–fragmentation chain transfer (PET-RAFT) polymerization, we successfully demonstrated, for the first time, the effective incorporation of AIE units into vinyl polymer backbones. The polymerization proceeds in a controlled manner, as evidenced by first-order kinetics and a linear increase in molecular weight with monomer conversion. This strategy is easily adaptable to a wide range of commercial vinyl monomers. The resulting polymers exhibit pronounced AIE behavior and can degrade under basic conditions. This methodology not only expands the synthetic toolbox for main-chain functionalization but also provides a versatile platform for designing next-generation vinyl polymers with inherent luminescent properties.

Ketenes constitute a versatile and highly reactive class of intermediates with widespread utility in modern organic synthesis. Among them, siloxyketenes, a class of oxygen-substituted variants, generated in situ from α-ketoacylsilanes through a photoinduced [1,3]-silyl migration, have garnered considerable attention due to their distinctive structural features. However, their synthetic utility has been confined to the construction of four- to six-membered rings. The development of methods that exploit these intermediates for the assembly of medium-sized rings remains exceedingly limited and is therefore highly desirable. Herein, we developed a metal-free, visible-light-driven [5 + 2] cyclization reaction for the synthesis of azepanone derivatives. Under irradiation of blue LEDs at 20 °C, α-ketoacylsilanes and vinyl aziridine were used as readily available substrates to realize this cyclization. The reaction features mild reaction conditions, operational simplicity, a broad substrate scope, and it generates diverse azepanones bearing a tertiary alcohol motif in good to excellent yields (up to 96%). The reaction proceeds via a photochemically induced [1,3]-silyl migration to form reactive siloxyketenes, followed by nucleophilic addition and a ring-closing process. This work expands the application of α-ketoacylsilanes as siloxyketene precursors and provides a concise and efficient approach to constructing medium-sized rings under mild conditions.

Substituted 1,2-diamines are common structural motifs in natural products and bioactive molecules, and their regioselective synthesis remains a pivotal challenge in organic chemistry. Herein, we report a Rh(III)-catalyzed directing group enabled unsymmetrical three- component diamination of alkenes (bearing thioether or amide directing groups), anilines, and dioxazolones for the efficient construction of 1,3-diamine derivatives. Under the optimized conditions, a broad range of anilines bearing electron-withdrawing substituents (e.g., –NO₂, –CF₃, –COOMe) are well tolerated, affording the desired products in moderate to excellent yields (61%–92%) with excellent regioselectivities (>20 : 1). Notably, anilines with electron-donating groups exhibit low reactivity, furnishing the desired products in poor yields. In contrast, the aryl ring of the thioether substrate can accommodate both electron-withdrawing and electron-donating groups without compromising reaction efficiency and selectivity. Additionally, both thioether and amide directed alkenes are compatible with the catalytic system. Mechanistic studies, including radical trapping experiments, control reactions, and high-resolution mass spectrometry analysis, reveal that the reaction proceeds through a sulfur- or amide-directed rhodacycle intermediate rather than an aziridine pathway. The directing group plays a key role in controlling both reactivity and regioselectivity by facilitating the formation of a stable five- or six-membered metallacycle intermediates. The synthetic utility of this methodology is further demonstrated by gram-scale synthesis and versatile derivatizations of the products, enabling the rapid construction of unsymmetrical diamine compound libraries. In summary, we have developed a Rh(III)-catalyzed protocol for the regioselective synthesis of unsymmetrical 1,2-diamines. This method features high regioselectivity, operational simplicity, and broad substrate scope, providing a practical and robust entry to structurally diverse diamines for applications in complex molecule synthesis and medicinal chemistry.

Fluorinated organoborons are highly valuable building blocks in drug discovery and materials science. However, the direct and step-economic synthesis of these complex structures remains a major challenge. Herein, we report a visible-light-driven, transition-metal-free chemodivergent borocarbonylation of α-trifluoromethyl styrenes. This multicomponent platform precisely controls the ultimate fate of the transient α-CF₃ benzylic radical. Under catalyst-free conditions, an electron donor-acceptor (EDA) complex with Hantzsch ester drives the radical cascade and a subsequent hydrogen atom transfer (HAT) to yield α-trifluoromethyl boronates. Alternatively, an Eosin Y/PMP photoredox system promotes a single-electron transfer (SET) and subsequent β-fluoride elimination to afford gem-difluoroalkenyl boronates. Overall, this strategy successfully manages the kinetic challenges of multi-step radical trapping, providing a practical and programmable platform to construct densely functionalized fluorinated organoborons.

This work reports the first example of rhodium-catalyzed asymmetric hydrogenation of 4-quinolone-2-carboxylic acids, providing direct access to chiral 2,3-dihydro-4-quinolones—a privileged scaffold in medicinal chemistry. Through systematic optimization of ligands, metal precursors, and solvents, the optimal catalytic system was identified as Rh(COD)₂OTf combined with the chiral bisphosphine ligand (R,R)-Ph-BPE. The reaction proceeds smoothly under 40 atm of H₂ in t-BuOH at 80 °C, affording a broad range of enantioenriched 2,3-dihydro-4-quinolones in moderate to excellent yields (40%–99%) and with high enantioselectivities (up to 99% ee). A broad range of substituents, including N-alkyl, N-benzyl, and electron-donating or electron-withdrawing groups on the quinolone core, are well tolerated, though the position and electronic nature of the substituents can affect enantioselectivity. Deuterium labeling experiments using D₂/t-BuOH and D₂/t-BuOD confirmed that molecular hydrogen (H₂/D₂) is the exclusive hydrogen source, with no direct participation of the protic solvent in the reduction step. Control experiments using C2-methyl or C2-ester substituted quinolones resulted in no conversion, demonstrating that the free carboxylic acid group is essential for substrate coordination to the rhodium center. Based on these findings and previous mechanistic studies, a plausible catalytic cycle is proposed involving oxidative addition of H₂, carboxylate-directed substrate coordination, migratory insertion into the C=C bond, and reductive elimination. Gram-scale reactions successfully delivered the desired products in high yields (92%–95%) and enantioselectivity (88% ee). Furthermore, product derivatization successfully furnished a new class of non-natural chiral amino esters, underscoring the synthetic utility of this method for constructing pharmaceutically relevant scaffolds.

Catalytic hydrogenation of carbon dioxide (CO₂) into aromatic hydrocarbons has emerged as a promising route for the high-value CO₂ utilization and sustainable aromatics production to alleviate fossil resource dependence under the carbon-neutrality goals. By integrating CO₂ activation/hydrogenation with the downstream C–C coupling and aromatization, bifunctional catalytic systems, typically comprising metal or metal oxide components coupled with acidic zeolites, enable the direct synthesis of valuable aromatics (e.g., benzene, toluene, and xylene) from CO₂. Recently, significant progress has been made in the rational design of such catalysts, particularly through the precise tailoring of the zeolite component for regulating the reaction pathways, product selectivity, and catalyst stability. This minireview summarizes recent advances in CO₂ hydrogenation to aromatics achieved by bifunctional catalysts, with a specific focus on the decisive role of the zeolite properties in governing the aromatization behaviors. Various zeolite modification strategies, such as acidity regulation, metal and non-metal functionalization, pore-structure engineering, and morphology control, are systematically discussed in relation to their effects on the intermediate transformation and aromatic selectivity. Finally, perspectives on future research are presented, emphasizing the importance of advanced characterization techniques and theoretical modeling for the rational design of more efficient, selective, and stable CO₂-to-aromatics catalysts and technologies.