Heteronuclear metal complexes have played an increasingly important role in both small molecules activation and catalytic transformation due to the potential metal-metal synergies. In this work, we reported that the well-defined Mg-Ni-Mg complex [( LMg) ₂Ni(C ₂H ₄) ₂] { L = [(DippNCMe) ₂CH] ⁻, Dipp = 2, 6- iPr ₂C ₆H ₃} was capable of catalyzing the conversion of a diverse array of terminal alkenes to hydrosilylated products in anti-Markovnikov fashion using PhSiH ₃ as the silicon source. The stoichiometric reaction of heterometallic Mg-Ni-Mg complex with one equivalent PhSiH ₃ obtained a silyl-nickel-monohydride complex [( LMg) ₂NiH(C ₂H ₄)(SiHPhEt)] featuring a Ni-Si-H-Mg interaction. Moreover, treatment of heterometallic Mg-Ni-Mg complex with three equivalents PhSiH ₃ provided the silyl-nickel-trihydride complex [( LMg) ₂NiH ₃(SiHPhEt)] with three hydride-bridged at Mg-Ni-Mg fragment. Further reactions of the resultant silyl-nickel complexes with alkenes, e.g., ethylene and styrene, yielded the corresponding alkene-coordinated Mg-Ni-Mg complexes [( LMg) ₂Ni(C ₂H ₄) ₂], [( LMg) ₂NiH ₂(C ₂H ₄)] and [( LMg) ₂NiH ₂(CH ₂CHPh)], respectively, with the elimination of PhEtSiH ₂. Based on the control experiments, both silyl-nickel-monohydride and silyl-nickel-trihydride complexes were considered as active intermediates in the catalytic hydrosilylation reaction.

Herein, we reported a precise de novo synthesis of chiral 3, 4-dihydroquinazoline frameworks via a one-pot anionic stereogenic-at-cobalt(III) complex-catalyzed enantioselective Ugi-azide/Pd-catalyzed cyclization sequence. This powerful protocol involves 5 components and 2 catalytic systems, delivering chiral 3, 4-dihydroquinazolines with excellent enantioselectivities (up to 94% ee). The preliminary antifungal experiments suggest that both Ugi-adducts and 3, 4-dihydroquinazolines have great potential in inhibiting plant pathogens such as Trichoderma viride and Fusarium graminearum.

The synthesis of N-glycosides has received significant attention due to their crucial role in carbohydrate chemistry. Despite considerable advancements developed in the construction of N-glycosides, methods for the stereoselective construction of 2-deoxy- α- N-glycosides are still limited. Herein, we disclosed a nickel-catalyzed hydroamination of glycals under mild conditions. This transformation could allow for the stereoselective synthesis of an array of 2-deoxy- α- N-glycosides with excellent α-stereoselectivity. Nickel-catalyzed glycosylation reactions, particularly those involving anomeric C(sp ³)-metal bond formation, have proven to be an effective and stereoselective strategy for producing various N-glycosides. Additionally, with highlight of the application of this reaction, γ-sugar amino acid derivatives were synthesized.

Side-chain engineering has emerged as a highly effective strategy for tailoring the aggregation behavior and charge transport properties of non-fullerene small molecule acceptors (SMAs). In this study, we designed and synthesized two SMAs, namely BTPSi-Bu and BTPSi-Pr, respectively incorporating tributylsilyloxy and triisopropylsilyloxy groups in their outer positions. Notably, BTPSi-Bu exhibited better planarity, crystallization, and favorable phase separation when paired with PM6 donor polymer compared to its counterpart, BTPSi-Pr. The resulting organic solar cells, utilizing the PM6:BTPSi-Bu blend, demonstrated a remarkable power conversion efficiency of 17.41% and a high open-circuit voltage of 0.859 V. These findings underscore the significance of integrating trialkylsilyloxy side chains into SMAs as a rational design approach for enhancing the performance of photovoltaic systems.

Transition-metal-catalyzed asymmetric alkylation of aldehydes represents a straightforward strategy for the synthesis of chiral secondary alcohols. However, efficient methods using organoborons as coupling reagents are rare. Herein, we report a highly enantioselective nickel-catalyzed alkylation reaction of aldehydes, using readily available alkylborons as nucleophiles. A wide variety of chiral secondary alcohols were prepared from commercially available aldehydes with high yields. The key to the excellent enantioselectivity and chemoselectivity was the employment of a bulky C ₂-symmetric chiral NHC ligand. This protocol features excellent enantiocontrol, mild conditions, and good functional group compatibility.

DNA 5-formylcytosine (5fC) is a prominent epigenetic modification within biological systems. Recent investigations have shed light on its pivotal role in governing cell fate, gene expression, and disease pathways. However, our comprehension of the precise control of the 5fC site structure to influence its functionality remains limited. In this study, we have successfully achieved precise control over 5fC activity by harnessing the interaction between streptavidin and biotin. This research underscores the potential application of interactions between biomacromolecules and small molecules in advancing the field of DNA epigenetic functional regulation.

The stability of organic radicals in ambient condition is important for their practical application. During the development of organic radical chemistry, the electron-withdrawing and steric hindrance groups are usually introduced to improve the stability of radicals via reducing the reactivity of radicals with oxygen in air. Herein, the electron-withdrawing carbonyl groups are introduced to construct a planar aromatic oxalic acid radical (IDF-O ₈) with two-dimensional electron spin pan structure. Interestingly, IDF-O ₈ exhibited a low optical bandgap of 0.91 eV in film, however, the multiple quinone resonance structures between electron-withdrawing ketone and phenol radicals contribute to the high stability of open-shell radical IDF-O ₈ without protection of large steric hindrance groups. Under the irradiation of 808 nm (1.2 W·cm ^–2), IDF-O ₈ reaches 147°C in powder state. This work provides an efficient synthesis route for the open-shell electron spin pan system, which is different from the famous fullerene, carbon nanotube and graphene. The electron spin pan can be extended to spin tube or spin sphere system based on the design strategy of aromatic inorganic acid radicals in future.

Hyperlanins A ( 1) and B ( 2), two highly rearranged polycyclic polyprenylated acylphloroglucinol (PPAP)-related meroterpenoids based on different new carbon skeletons, were isolated from Hypericum lancasteri. Compound 1 incorporates an unprecedented 5/6/7/5 ring system featuring a 3, 13-dioxatetracyclo[9.2.1.1 ^{2, 5}.0 ^{1, 8}]pentadecane core. Compound 2 possesses a unique compact 6/6/5/6/6/5/6 ring system with a caged tetracyclo[6.2.1.1 ^{3, 8}.0 ^{5, 11}]dodecane motif. Their structures were established by spectroscopic data, X-ray diffraction, and computational approaches. Both compounds showed anti-inflammatory activity in vitro. Compounds 1 and 2 could decrease the lipopolysaccharide (LPS)-/nigericin-induced IL-1 β release in THP-1 cells. Both compounds also showed inhibition in hypoxia-inducible factor-1 α (HIF-1 α) pathway luciferase reporter assay.

Redox nanozymes offer an appealing reactive oxygen species (ROS)-based antibacterial strategy via disrupting intracellular homeostasis, however, they still face many obstacles such as low enzymic activity and irreversible loss of catalytic active center. Meanwhile, the antioxidant glutathione (GSH) overexpressed in infected sites would limit the therapy efficiency. Herein, we develop a multifunctional nanozyme based on copper(I) (Cu ⁺) ion doped MoO _3– x (Cu ⁺-MoO _{3– x}) by a simple yet efficient oxygen vacancy-reduced strategy without any pretreatment or additional agents. The resultant Cu ⁺-MoO _{3– x} hybrid possesses enhanced peroxidase-like (POD-like) activity, rapid GSH-depleting function and biodegradable ability. It can achieve highly efficient elimination of Pseudomonas aeruginosa ( P. aeruginosa) via disrupting cellular redox balance. More intriguingly, GSH-depleting redox reaction between Cu ⁺-MoO _{3– x} and GSH could translate Mo ⁶⁺ into Mo ⁵⁺, thereby leading to partial recovery of POD-like activity of Cu ⁺-MoO _3– x hybrid for continuous ∙OH generation. In vitro and in vivo experiments demonstrated that Cu ⁺-MoO _{3– x} hybrid had stronger antibacterial property compared to MoO _{3– x} by rapid GSH consumption and plentiful ^∙OH generation without providing extra H ₂O ₂, as well as neglective toxicity to healthy organs. In view of its remarkable enzymic activity and good biosafety, the developed Cu ⁺-MoO _{3– x} redox nanozyme can be used as a promising antimicrobial for P. aeruginosa infection.

An efficient and highly stereoselective synthetic method to access polycyclic chromanes has been achieved through organocatalyzed one-pot step-wise reactions involving 2-hydroxycinnamaldehydes, 2-aminochalcones, and malononitrile as substrates. The reactions underwent a quintuple process by aza-Michael/Michael/Knoevenagel/oxa-Michael/aldol-type reaction in sequence to give products bearing 3 new generated rings and 5 chiral centers in moderate to quantitative yields with excellent stereoselectivities. A novel retro-reaction mechanism was discovered in the synthetic transformations of products.

Compared to well-established 1, 5-HAT of N-centered radicals, the synthetic applications of 1, 2-HAT process were scarce due to the high barrier and constrained three-membered transition state. Here, we have developed a novel C(sp ³)-H gem-difluoroallylation via a base assisted formal 1, 2-HAT of amidyl radicals with the reductive quenching cycle of photocatalyst. This transformation enables the efficient formation of α-aminoalkyl radicals via 1, 2-HAT and showcases good functional group tolerance. Our preliminary mechanistic experiments, along with Density Functional Theory (DFT) calculations demonstrate the feasibility of 1, 2-HAT of amidyl radicals, especially when assisted by a base. Furthermore, our method also succeeds in the Giese addition of electron-deficient alkenes as well as styrene.

Although it offers a direct route to access synthetically valuable α-chiral primary amines, asymmetric transfer hydrogenation of NH imines has been rarely studied, due in large part to the inaccessibility and instability of NH imines. Herein, we report a Rh-catalyzed asymmetric transfer hydrogenation of a kind of novel and stable NH imines which are prepared via condensation of easily available sulfonylated 2’-aminoacetophenones with NH ₃ in methanol. With this method, enantioenriched chiral 2-(1-aminoalkyl)anilines, which are privileged pharmacore groups, have been synthesized with good functional group compatibility, and with up to 99% ee. A gram-scale reaction using 0.2 mol% of catalyst has been successfully performed to highlight the practicality. Furthermore, the products can be derivatized into enantiopure bioactive molecules as well as chiral tridentate ligands for metal catalysis.

In this paper, the difunctionalizative perfluoroalkyloximation of alkenes has been developed for the first time. This photochemical method allows for the synthesis of various perfluoroalkyl ethanone oximes with excellent regioselectivity and good functional group tolerance. Our method employs the most common perfluoroalkyl source, perfluoroalkyl iodides, as R _f reagents. Besides long-chain perfluoroalkyl groups, this approach could be extended to incorporating additional groups, including trifluoromethyl, difluoromethyl, sulfonyl, and malonate, selectively into olefins, resulting in a range of β-substituted ethanone oximes. Notably, the potential of this method in the Fukuyama indole synthesis, generating novel 2-perfluoroalkylated 3-(α-oximidobenzyl)indoles via a radical cascade mechanism with 2-vinylphenylacryloyl isocyanate as the radical acceptor, presents a compelling avenue for drug synthesis. The protocol is efficient, scalable, and useful for late-stage modification of bioactive molecules.

Allenes, served as highly sought-after building blocks, are an indispensable component of synthetic chemistry. Their utility in modulating the chemical, physical, and pharmaceutical properties of organic compounds make allenes a desirable choice in various applications. Here, we report a facile method for the atom-economical synthesis of propargyl allenylamines via an underdeveloped [2, 3]-sigmatropic rearrangement. Our strategy employs easily accessible propargylamines as starting materials, which are first converted into propargyl ammonium salts, followed by a base-promoted [2, 3]-sigmatropic rearrangement. This one-pot, two-step reaction proceeds in the absence of transition metals, displays a very broad scope, and does not require the introduction of the electron-withdrawing group into the starting materials.

Unsymmetrical diarylamines are crucial components in many pharmaceuticals and functional materials. In this study, we introduce an efficient Chan-Lam cross-coupling method that utilizes phenylboronic acids and aryl azides as coupling agents in a redox-neutral environment, enabled by a synergistic nickel/photoredox catalytic system. This approach leverages a proton-coupled electron transfer mechanism to bypass the typical nitrene pathway associated with aryl azides, which is prone to intramolecular rearrangement, C—H amination, and reductive hydrogenation. Notably, our method exhibits broad compatibility with a variety of functional groups, including those derived from pharmaceuticals, demonstrating its versatile potential in organic synthesis and drug modification.

A visible-light-induced photoredox-catalyzed regioselective and stereoselective C(sp ²)–H amination of enamides with bench-stable and easily accessible N-aminopyridium salts is developed, affording synthetically and biologically prominent vicinal 1, 2-diamine scaffolds with broad substrate scope and excellent functional group compatibility. The transformation proceeded through a radical pathway involving the Giese addition of the relatively electrophilic N-centered sulfonamidyl radical species to nucleophilic β-olefinic position of enamides followed by the ensuing single electron oxidation and β-H elimination, delivering geometrically-defined Z-configured β-sulfonamidylated enamides. The operational simplicity, environmental friendliness and cost efficiency of this methodology allowed it to pave a new avenue to enrich the arsenal of synthetically crucial functionalized enamides and their related derivatives.

Herein, we report rhodium catalyzed N-arylation via addition of arylboronic acids to electron-deficient α-iminoesters which can be prepared in high efficiency by using easily accessible β-carbonyl esters. The reaction is highly regiospecific to achieve the N-aryl addition efficiently with up to 99% yield under mild conditions. The corresponding product can be further efficiently converted into indoles and a series of other important building blocks.

CO ₂ is an abundant, nontoxic, and renewable C1 feedstock in synthetic chemistry. Direct carboxylation of readily available olefins incorporating CO ₂ is regarded as a promising strategy to access high value-added carboxylic acids as well as CO ₂ fixation. However, due to the thermodynamic stability and kinetic inertness of CO ₂ and the difficulty in controlling the regioselectivity, the carboxylation of olefins with CO ₂ still remains challenging. Radical-type functionalization with olefins represented a powerful protocol and enabled the development of novel transformations in this realm. More recently, the advance of new technology, such as photoredox catalysis and the renaissance of electrochemistry in organic synthesis, offered access to unique chemical reactivities of radical precursors and provided new solutions to the functionalization of olefins. This review presents the recent advances in the radical-type carboxylation of olefins, which has mainly been achieved through photocatalysis and electrocatalysis in the last decade. In this article, we provide a comprehensive introduction of the progress, summarize the advantages and limitations of current research, and discuss the potential outlook for further development.