We herein report a Pd(0)-catalyzed Catellani-type reaction of aryl iodides, O-acylhydroxylamine, and norbornadiene (NBD), where NBD acts as an o-tolyl synthon to efficiently afford aminobiphenyl derivatives. The key to this transformation is a rare β2-carbon elimination of the norbornyl Pd(II) intermediate rather than the classic β1-carbon elimination, making this the first example of NBD as an aromatic synthon in a Catellani-type reaction.

An intramolecular α-C(sp3)-H phenoxylative cyclization of thioethers is developed using phenols as intramolecular nucleophiles and Selectfluor as a mild oxidant, thereby efficiently constructing seven-membered S,O-heterocyclic scaffolds with high efficiency and excellent functional group tolerance. This phenoxy-Pummerer transformation expands the tool box for α-C(sp3)-H functionalization of thioethers, which provides a new paradigm for incorporating oxidation-sensitive nucleophiles under mild conditions.

While the thiosulfonylation of C─C π-bonds is well-established, the analogous functionalization of kinetically inert C─C σ-bonds remains a formidable challenge, particularly regarding stereoselective control. Herein, we report a general photocatalytic strategy for the chemo- and stereoselective 1,3-thiosulfonylation of cyclopropylamides. This method successfully addresses the elusive challenge of stereocontrol in σ-bond thiosulfonylation, enabling the unprecedented asymmetric construction of metastable γ-thio-α-aminosulfones with excellent enantioselectivity. The optimized protocol exhibits a broad scope, accommodating a diverse array of cycloalkylamides as well as mono-, di-, and even trithiosulfonates. Furthermore, the utility of this methodology is highlighted by its successful application in the late-stage functionalization of pharmaceutically relevant compounds, diverse downstream transformations. Most crucially, we have demonstrated that the resulting chiral ɑ-amidoalkylphenyl sulfones readily undergo stereoselective substitution in SN2-like pathway, effectively outcompeting the typically predominant E2-type elimination process.

A strategy based on sequential "C-H thianthrenation/Pd-catalyzed asymmetric Heck reaction" was designed to synthesize trisubstituted chiral allenes from nonprefunctionalized arenes directly. This innovative approach successfully addressed challenging cyclic and acyclic systems while enabling the late-stage modification of complex small molecules. The methodology exhibited remarkable robustness through its successful implementation in a gram-scale reaction and the recycling of thianthrene. Density functional theory computation results reveal that the enantioselective step follows a base-accelerated β-H elimination mechanism.

We herein report a palladium-catalyzed cascade reaction that enables the de novo synthesis of spirooxindoles from simple ortho-iodoaniline derivatives, in which tertiary O-benzoyl hydroxylamines serve as bifunctional single-nitrogen sources through sequential C-H diamination and C-N activation. The reaction features a broad substrate scope and accommodates both diamination and triamination pathways. Preliminary asymmetric studies afford the desired product in up to 92% ee, providing a concise route to structurally diverse spirooxindoles.

Boron-stereogenic BODIPYs represent an emerging class of chiral fluorophores with promising applications in materials science and bioimaging; however, their enantioselective synthesis, particularly for multiply substituted variants, remains highly challenging. Herein, we report an enantioselective Catellani desymmetrization strategy that enables efficient access to structurally complex boron-stereogenic BODIPYs. The reaction delivers a broad range of products (87 examples) with excellent enantioselectivity (up to 99% ee) and high chemoselectivity. The method tolerates diverse functional groups and provides versatile scaffolds for further derivatization without a loss of enantiopurity. Moreover, the resulting BODIPYs exhibit tunable photophysical properties and efficient cellular uptake, highlighting their potential use in optoelectronic and bioimaging applications.

Dalesconols A and B, featuring unique and highly congested polycyclic carbon frameworks and notable biological activities, have attracted sustained attention. However, their structural complexity constitutes a significant challenge for total synthesis. Herein, we present the asymmetric total syntheses of (+)-dalesconols A and B via a remote chirality transfer strategy. Central to this approach is the implementation of our palladium/norbornene-catalyzed trifunctionalization method, which enables one-step construction of the chiral polycyclic core skeleton via a triple relay of point-to-axial, axial-to-axial, and axial-to-point chirality transfer. Combined with intramolecular Michael addition, C-H oxidation/retro-Michael elimination, and global demethylation, this triple-relayed remote chirality transfer strategy allows concise and modular access to (+)-dalesconols A and B.

image [118‐52‐5] C 5 H 6 Cl 2 N 2 O 2 (MW 197.02) InChI = 1S/C5H6Cl2N2O2/c1‐5(2)3(10)8(6)4(11)9(5)7/h1‐2H3 InChIKey = KEQGZUUPPQEDPF‐UHFFFAOYSA‐N 1,3‐Dichloro‐5,5‐dimethylhydantoin (DCDMH) is a disinfecting agent and bleaching agent that has been extensively used as a disinfectant for industrial and domestic water. 1 In contrast to common disinfectants, DCDMH does not have the odor of chlorine and is barely irritating to human beings. A mild chlorinating reagent with the capability of selective chlorination. Alternate Name: DCDMH; 1,3‐dichloro‐5,5‐dimethylimidazolidine‐2,4‐dione; 1,3‐dicholo‐5,5‐dimethyl hydantoin. Physical Data: bp 214.7 °C at 760 mmHg, mp 132 °C, d 1.50 g cm −3 . White powder, slightly soluble in water, with a faint pungent odor. The substance exhibits slight solubility in water, with a solubility value of 1.98 g L −1 at 20 °C. It is prone to moisture absorption and undergoes partial hydrolysis. Analysis of Reagent Purity: 1,3‐dichloro‐5,5‐dimethylhydantoin gives a singlet in 1 H NMR at δ 1.55, with 13 C absorption at δ 169.95, 150.43, 68.06, 22.62, and 19.32. Preparative Methods: this reagent can be synthesized by reacting 5,5‐dimethylhydantoin with chlorine gas under alkaline conditions or with sodium hypochlorite under low‐temperature, neutral conditions, achieving a yield of 94–96%. Handling, Storage, and Precautions: keep in dark place, sealed in dry, room temperature. Strong oxidizer. Incompatible with combustible materials, reducing agents, acids, and strong bases. Moisture‐sensitive. Toxicity (oral) rat LD 50 : 542 mg kg −1 .

Dearomatization of planar aromatics offers unparalleled opportunities for the construction of three-dimensional stereochemical frameworks. However, the inherent instability of dearomatized intermediates, particularly bearing labile C(sp3)-heteroatom bonds, has hindered progress due to competing rearomatization pathways. By capitalizing on arene dearomatization and transforming the rearomatization predicament into a new opportunity, we herein present a stability-driven catalytic asymmetric dearomatization/rearomatization (CADA/RA) cooperative strategy to resolve racemic P-stereogenic compounds. Through the systematic engineering of phenolic substrates, bench-stable P-site dearomatized products with dual C(sp3)-P and C(sp3)-Cl bonds were isolated. Chiral Lewis acid catalysis enabled kinetic resolution (KR) and parallel kinetic resolution (PKR), achieving full enantiomeric separation with exceptional stereocontrol across diverse substrates. Mechanistic analysis revealed competing substrate- and catalyst-controlled pathways for stereochemical precision. Postsynthetic chemoselective Cl- or P-liberation furnished enantioenriched P-chiral compounds. This method transforms the challenges of dearomatization and rearomatization into opportunities for stereochemical complexity generation, offering a robust platform to synthesize P-chiral building blocks and ligand precursors.

Selective functionalization of unactivated C─C and C─H bonds in mono-donor cyclopropanes represents a significant yet challenging goal in organic synthesis. Although numerous reported studies have documented the 1,3-difunctionalization of these substrates, effective strategies for 1,2-difunctionalization have so far proven elusive. Herein, we report a novel catalytic strategy enabling the 1,2-difunctionalization of mono-donor cyclopropanes. By merging of organophotoredox and cobalt catalytic system, this method achieves selective ring-opening and homobenzylic oxygenation, facilitated by a two-fold sequence involving single electron transfer, nucleophilic addition, and acceptorless dehydrogenation. This unprecedented process overturns the predominant 1,3-selectivity in mono-donor cyclopropane functionalization, concurrently establishing a streamlined platform for forging β-aryl-α′-oxyketone derivatives in a sustainable manner.

Polyfunctionalized chiral biaryls, especially those with dense ortho substitution patterns, are important building blocks for catalysts, pharmaceuticals, and advanced materials. Stereoselective synthesis of these congested architectures while simultaneously introducing multiple sites for further modification is highly sought after. Here, we report that a combination of an aziridinyl methanol-derived tetradentate ligand and a lithium cuprate salt can differentiate between the pair of aldehydes in biaryl isophthaldehydes to enable a desymmetric hydrosilylation. The bimetallic synergy within the ligand pocket delivers excellent enantiocontrol not only for structurally diverse tri-ortho-substituted isophthaldehydes from axis-forming cross-coupling but also for polyaldehydes prepared via the "plane-to-axis" ozonolysis of pyrenes. This strategy further exploits the reactivity of the resulting primary alcohol and remaining aldehyde to accommodate divergent postreduction transformations. Notably, the bismethylene-biaryl product generated by desymmetrization, with its four readily modifiable ortho positions, offers modular access to biaryl frameworks bearing diverse functionalities and structural features for broad applications.

A Selectfluor-mediated protocol for the direct synthesis of aryl sulfinate esters from aryl alkyl thioethers is reported. This reaction is initiated by Selectfluor-promoted C(sp3)-S bond cleavage and engages the substrate in a formal stepwise oxidation process to furnish aryl sulfinate esters. This method operates under mild conditions, tolerates diverse functionalities, and provides efficient access to synthetically valuable sulfinate scaffolds.

We herein report a unified strategy integrating catalytic asymmetric chlorinative dearomatization and stereoselective dechlorinative rearomatization for resolving axially chiral 1-aryl-2-naphthols. By using a Sc(III)/Py-BOX catalytic system, naphthol-based biaryls underwent kinetic resolution through asymmetric chlorinative dearomatization. This process converted the intrinsic C(sp2)-C(sp2) axial chirality of one enantiomer into a conformationally favored C(sp2)-C(sp3) axis by generating a chlorine-containing C(sp3)-stereogenic center. The reaction showed high functional group tolerance and excellent enantioselectivities across a wide range of substrates. Subsequently, a stereospecific rearomatization protocol using triethylamine under blue-light irradiation was developed. This dechlorination method exploited an electron donor-acceptor (EDA) complex mechanism, efficiently converting the stored C(sp2)-C(sp3) axial chirality back to the original C(sp2)-C(sp2) axis, thus enabling full resolution of the biaryl atropisomers. The resolved 1-aryl-2-naphthols can be readily transformed into various catalytically and synthetically valuable molecules, such as axially chiral monophosphine, bisphosphine, aldehyde, and carboxylic acid.

Herein we report a novel palladium/norbornene-catalyzed trifunctionalization reaction of ortho -unsubstituted iodoarenes by incorporating two distinct acyl groups at their ortho C─H positions and replacing the ipso -iodide with an alkenyl or aryl group. Notably, this transformation was enabled by the alkyl/aryl mixed anhydrides, which were utilized as dual acylation reagents by abstracting their central oxygen atom with electrophilic 2-chloro-4,6-dimethoxy-1,3,5-triazine. Mechanistic studies revealed that the alkyl-acyl unit of such an anhydride was employed for the first C─H alkyl-acylation, and in situ released aryl carboxylate anion was then rapidly activated with triazine chloride to provide an aryl–acyl electrophile for the second C─H acylation, thus enabling the trifunctionalization of iodoarenes by termination with an intermolecular Heck or intramolecular arylation reaction. In addition, the synthetic utility of this method is exemplified by the selective manipulation of carbonyl groups of the products.

Northwest University,as a regional comprehensive university,has pioneered a distinctive "progressive" integrated training mode for innovative chemistry talents to address the key educational challenges in Western China. This model condensed the spirit of "Lights of chemistry and materials" to motivate hard work and innovation. It constructed a "three-focus" path of ideological and political education,consisting of "value leadership,cognitive development,and character molding". It also established a "three-in-one" integrated training system,characterized by "three dimensional curriculum system-systematic professional training-open and innovative practice". Additionally,a holistic quality assurance system involving the university,college,society,mentor,and student termed the "five-in-one" quality assurance strategy,has been implemented. This innovative model not only caters to various degree levels and disciplinary backgrounds,but also robustly supports the socio-economic advancement of Western China. This paper introduces the measures and achievements of the reform in graduate education at Northwest University in the field of chemistry.

Herein, we present a practical strategy for the asymmetric synthesis of chiral acyclic nitriles featuring alpha-all-carbon quaternary stereocenters, utilizing synergistic palladium and phase-transfer catalysis from allyl 2-cyanoacetates under mild conditions. This approach offers an efficient and reliable method for the in situ generation of tertiary alpha-cyano carbanions through intramolecular palladium-catalyzed decarboxylative allylic alkylation. Additionally, it enables highly enantioselective control of simple nitriles via ion-pairing interactions with chiral phase-transfer catalysts. The synthetic utility of this method is further demonstrated by its scalability to gram-scale synthesis and its subsequent transformation into a variety of chiral functionalized compounds containing acyclic all-carbon quaternary stereocenters.

We disclose herein a novel photoredox and cobalt co-catalyzed ring-opening/acceptorless dehydrogenative functionalization of mono-donor cyclopropanes. This sustainable and atom-economic approach allows the rapid assembly of a wide range of allylic N,O-acyl-acetal derivatives. The starting materials are readily available and the reaction features mild conditions, broad substrate scope, and excellent functional group compatibility. The optimized conditions accommodate assorted cycloalkylamides and primary, secondary, and tertiary alcohols, with applications in late-stage functionalization of pharmaceutically relevant compounds, stimulating further utility in medicinal chemistry. Moreover, selective nucleophilic substitutions with various carbon nucleophiles were achieved in a one-pot fashion, offering a reliable avenue to access some cyclic and acyclic derivatives.

A silver-catalyzed aminative dearomatization of naphthols has been developed and integrated into a stepwise approach for subsequent skeletal diversifications including ring expansion, ring opening, ring contraction, and atom transmutation of aryl scaffolds. This approach enables the synthesis of a diverse array of azepinones, unsaturated amides, isoquinolines, and indenones from naphthol substrates. Its application in the synthesis of bioactive and functional molecules as well as the conversion of complex molecular skeletons underscores its broad potential applicability. Mechanistic investigations suggest the intermediacy of the dearomatized intermediates.

A novel [4 + 1] and [5 + 1] dearomative spiroannulation has been developed by the use of commercial naphthols and phenols with dielectrophiles. Various spirocycles, including spiro[4.5] and spiro[5.5] have been constructed successfully by employing four-atom or five-atom dielectrophilic synthons. This transformation was realized through a sequence of site-selective C-alkylation/dearomative spiroannulation. Moreover, the potential application of this method was exemplified by several further transformation.

Herein, we disclose a novel reorganization/cycloaddition between two imine units catalyzed by In(OTf)(3) Lewis acid that differs from the well-known [4 + 2] cycloaddition version via the Povarov reaction. By means of this unprecedented imine chemistry, a collection of synthetically useful dihydroacridines has been synthesized. Notably, the obtained products give rise to a series of structurally novel and fine-tuneable acridinium photocatalysts, offering a heuristic paradigm for synthesis and efficiently facilitating several encouraging dihydrogen coupling reactions.