Organic phosphorus compounds containing sp³-C—P(O) bonds are increasingly widely applied in catalysis, pharmaceuticals, materials, pesticides, and other fields, and their synthesis has become a research hotspot in chemistry. Diarylmethyl phosphine oxides are important organic phosphorus compounds containing sp³-C—P(O) bonds, but their synthesis is limited. Traditional methods for their synthesis require the use of halogenated compounds and harsh reaction conditions. A new method for the copper-mediated synthesis of (diarylmethyl)diarylphosphine oxides has been developed. This method involves the cleavage of the sp³-C—N bond in N-diarylmethylsulfonamides, leading to the formation of diarylmethyl carbocations. The carbocations then react with diarylphosphine oxides to construct sp³-C—P(O) bonds. Our method only requires the addition of stoichiometric, inexpensive CuBr₂ and produces a series of target compounds in satisfactory yields. Thus, it provides a convenient, and cost-effective pathway for the synthesis of diarylmethyl phosphine oxides.

This paper aims at developing a highly enantioselective ruthenium-catalyzed asymmetric hydrogenation of ena- mine ester to synthesize the chiral intermediate of sitagliptin. Through a comprehensive investigation of ruthenium catalyst precursors, chiral ligands, acids and ammonium salts as additives, temperature, pressure, and solvent, (R)-3-amino-4-(2,4,5- trifluorophenyl) isopropyl butyrate, the key intermediate of sitagliptin, was obtained in 97% yield and 99% ee by asymmetric hydrogenation from β-2,4,5-trifluorophenyl-β-enamine ester under the action of Ru-BIBOP catalyst, with p-toluenesulfonic acid and ammonium p-toluenesulfonate as additives, and dichloromethane/methanol as solvent, under 5 MPa of hydrogen pressure and 60 ℃ for 22 h. The use of Ru-BIBOP catalyst plays a key role in achieving high enantioselectivity for this trans- formation.

An organophosphoric acid catalyzed [3＋3] cyclization of 2-arylidene-indan-1,3-diones with enaminones has been established, which afforded a series of structurally diverse indenoquinolinedione derivatives in moderate to excellent yields. This [3＋3] cyclization has some advantages such as mild reaction conditions, readily available catalyst and wide substrate range. This work not only provides an efficient method for constructing biologically important 1,4-dihydropyridine motif, but also suggests a possible reaction pathway and activation mode, therefore enriching the research contents of organophosphoric acid catalysis and [3＋3] cyclization reactions.

Phosphine-catalyzed [5＋1] annulation reaction of Morita-Baylis-Hillman (MBH) carbonates with 1,3-dicarbonyl compounds has been developed, producing biologically interesting spirocyclohexene derivatives in high yields with moderate to excellent diastereoselectivities. The annulation was achieved through sequential 1,6-conjugate addition/nucleophilic substu- tion reaction of phosphine ylides with dinucleophiles.

Cesium carbonate was used as a base to achieve the desulfurization reaction of alkenyl sulfonium salts and phosphine oxides at room temperature, forming C(sp²)—P bonds. This method features simple operation, mild reaction conditions, and good functional group compatibility, offering a straightforward and efficient preparation route for terminal vinyl phosphine oxides.

Tertiary phosphines and their oxides react with oxalyl bromide to generate corresponding quaternary phosphonium salts, which can be further transformed as active intermediates to facilitate the bromination of alcohols and the dibromination of unsaturated hydrocarbons. This chemical process carries substantial research significance in the field of organic synthesis. In this study, two types of triaryl phosphine oxides and benzyl diaryl phosphine oxides containing alkyne groups were designed and synthesized. These compounds were then subjected to reaction with oxalyl bromide, resulting in the formation of novel benzophosphonium tribromides and trans-phosphoryl dibromoalkenes, respectively. These findings demonstrate variations from their reactions with oxalyl chloride. Furthermore, the benzophosphonium tribromide obtained can act as an alternative reagent for bromine, enabling the direct bromination of aromatics compounds, olefin, alkyne and acetophenone derivatives.

A [4＋4] annulation reaction for the construction of medium-sized N-heterocycles is reported. This process involves the generation of all-carbon 1,4-dipoles containing a π-allylpalladium complex from Morita-Baylis-Hillman (MBH) carbonates under the catalysis of Pd/Synphos, which then undergo Michael addition/N-allylic alkylation with 1-azadienes. A spectrum of eight-membered N-heterocycles featuring a trisubstituted exo-cyclic double bond is furnished efficiently with moderate to good E/Z selectivity and moderate atroposelectivity. In addition, moderate enantioselectivity can be realized by using a chiral ligand or with the assistant of a chiral quaternary ammonium salt.

Binaphthalene-core phosphepine compounds with axial chirality belong to an important class of organocatalysts and ligands used in catalytic asymmetric synthesis. However, the number and application of these compounds have been limited due to the lack of efficient synthetic methods currently available to researchers. Herein, a simple and efficient palladium-catalyzed C—P cross-coupling reaction of enantiopure (R)-1 with a variety of aryl and heteroaryl halides is reported. The reaction provides access to a series of chiral binaphthalene-core phosphepine compounds using Pd(OAc)₂/dippf as a catalyst, which allows most products to be formed in moderate to high yields (40%~92%) with excellent ee values (90%~99% ee).

Near-infrared (NIR) luminescent materials have great potential in the field of bioimaging due to their unique advantages of strong tissue penetration and weak light scattering in biological tissues. In this study, a donor-acceptor (D-A) structured boron difluoride β-diketonate complex (TPA-BF₂-CN) was designed and synthesized through the strategy of enhancing intramolecular charge transfer. This complex exhibits solvent-dependent luminescent properties. It demonstrates good luminescence efficiency in dilute solution and solid state with efficiencies of 11.1% and 5.9%, respectively. The maximum emission wavelength peaks at 760 nm, falling within the NIR range. The complex also possesses mechanochromic properties with a redshift of emission wavelength by 107 nm after grinding. TPA-BF₂-CN exhibits dual emission fluorescence phenomenon with emission peaks located in the blue light region at 400 nm and the NIR region at 760 nm with an emission wavelength range of 690~850 nm in the NIR region. Compared to single-channel fluorescent molecules, it has the advantage of avoiding interference from environmental factors. Cell imaging studies demonstrate good compatibility of TPA-BF₂-CN with HeLa cells, and NIR emission signals can be observed throughout the cytoplasmic region of HeLa cells. Therefore, TPA-BF₂-CN can serve as a fluorescent probe for live cell imaging.

Under the catalysis of 20 mol% Cs₂CO₃, β-(2-hydroxyaryl) ethenesulfonyl fluorides reacted with ketoesters throu- gh a tandem intermolecular/intramolecular Michael addition process at room temperature, affording 11 multisubstituted 4H- chromenes bearing a useful sulfonyl fluoride groups in 56%~70% yields. In addition, under the mediation of 50 mol% Cs₂CO₃, β-(2-hydroxyaryl) ethenesulfonyl fluorides couple with ynones through a similar tandem process at 50 ℃, giving 12 multisubstituted 4H-chromenes in 25%~80% yields.

1,4-Naphthoquinone, as a core skeleton exists in many bioactive molecules and has a wide range of applications in medicine, biology, cosmetics, and other synthetic materials. A photochemically synthetic method for aminoaryl bifunctionalized 1,4-naphthoquinone compounds by using 1,4-naphthoquinone, amine, and aryl triazene as raw materials is developed. This method features the advantages of simple and easy to operate without the need for any metals, extra oxidants, or other additives. It only requires methanol as the solvent and purple LED irradiation to efficiently synthesize aminoarylated 1,4- naphthoquinone derivatives. The smooth progress of gram scale reactions further proves the practicality of this method.

The efficient total synthesis of trans-4'a-methyl-3',4'a,9',10',10'a-hexahydro-spiro[cyclobutane-1,1'(2H)- phenanthrene] has been accomplished starting from commercially available 3-phenylpropanal by two routes which take Au-catalyzed 1,3-acyloxy migration/cyclization cascade and InI₃-catalyzed polyene-type cyclization as the key synthesis steps, respecti- vely.

Polyanilines (PANIs) are widely employed materials that are synthesized via the oxidative polymerization of anilines. However, the present synthetic methods always require the use of chemical oxidants and employ HCl/NaOH as the acid-base regulator, resulting in a large amount of waste salt and residual impurities in the material that affect its performance. These drawbacks are unfavorable for industrial applications. A novel method for the preparation of PANIs, i.e. the Se/ZrO₂- catalyzed oxidative polymerization of aniline with O₂ free of the acid-base regulator is developed. The relatively safe and green features of the method make it more practical for large-scale applications. Researches showed that PANIs prepared by this method could be used as the support to anchor palladium catalyst, and its activity was as good as that of the materials synthesized via traditional methods.

Salicylaldiminato neutral nickel catalysts is a family of classic ethylene polymerization catalysts. Through elabrate modulation of the structures, various polyethylene materials with different characteristics can be prepared, such as highly branched polyethylene oil and ultra-high molecular weight polyethylene with low branching. However, these catalysts face certain challenges in the preparation of elastomeric materials. In this study, two arylamines containing both sterically hindered groups and adjacent heteroatom groups were designed and synthesized for the synthesis of salicylaldiminato ligands and the corresponding neutral nickel catalysts ({N-[2,4-bis(dibenzosuberyl)-6-phenoxy]phenyl-3-tert-butylsalicylideneiminato}-nickel(II)-(phenyl)(triphenylphosphine) (Ni2) and {N-[2,4-bis(dibenzosuberyl)-6-benzenesulfonyl]phenyl-3-tert-butylsalicyli- deneiminato}-nickel(II)-(phenyl)(triphenylphosphine) (Ni3)). The effects of temperature and ethylene pressure on catalytic performance were systematically investigated, revealing the variation patterns of catalyst thermal stability, catalytic activity, polymer molecular weight and branching density. The combination of the secondary coordination effect of the heteroatom groups and the steric effect of the arylamine allowed catalyst Ni3 containing SO₂Ph group to achieve a balance between branching density (61 brs/1000C) and polymer molecular weight (M_n=15.29×10⁴), providing strong support for the preparation of polyethylene elastomer with excellent mechanical properties. The synergistic effect of steric hindrance and secondary interaction provides new ideas for the development of novel salicylaldiminato neutral nickel catalysts and the design and optimization of related catalysts.

3,5-Diarylpyridines were effectively synthesized via [2＋2＋1＋1] cyclization reaction catalyzed by Fe(OTf)₃ at 140 ℃, using phenylacetylenes or phenylacetaldehydes, ammonium chloride and N,N-dimethylethanolamine as starting materials. N,N-Dimethylethanolamine was employed as both solvent and a single carbon synthon.

Dipeptidyl peptidase IV (DPP-IV), a transmembrane glycoprotein overexpressed in cancer cells, is often used as an important biomarker for early detection of tumors. A near-infrared turn ON fluorescence probe (MB-DPP) was developed for the sensitively detection of DPP-IV in liver cancer cells. MB-DPP employs methylene blue as fluorophore and p-aminobenzyl alcohol as the connecting arm to bond glycyl-L-proline as the specific cleavage site of DPP-IV through dehydration condensation reaction, thereby achieving the fluorescence “turn on” reaction triggered by DPP-IV. Probe MB-DPP emits strong near-infrared fluorescence at 691 nm after the incubation with DPP-IV. Spectral experiments showed that MB-DPP exhibited high selectivity and detection sensitivity (with a detection limit of 1.12 ng/mL) for DPP-VI. Bio-imaging studies showed that MB-DPP could not only achieve fluorescence imaging analysis of DPP-IV activity in liver cancer cells, but also be used for imaging of DPP-IV in liver cancer tumors. Therefore, the development of probe MB-DPP will contribute to the early diagnosis of liver cancer.

A copper-catalyzed Sonogashira coupling reaction and 5-exo-dig aminocyclization between 2-(2-bromophenyl)- benzofuro[3,2-d]pyrimidin-4(3H)-ones and terminal alkynes were disclosed. The protocol allowed access to a series of 8-benzylidene benzofuro[3',2':4,5]pyrimido[2,1-a]isoindol-6(8H)-one derivatives with high efficiency, broad substrate scope, and excellent functional group compatibility, which were shown to be of a single (E)-configuration by X-ray diffraction analysis.

Mechanochemical synthesis of 3-substituted 2-indolymethanols through scandium(Ⅲ)/palladium(Ⅱ) synergistic catalyzed Friedel-Crafts alkylations of donor-acceptor cyclopropanes and 2-indolymethanols has been developed. A wide broad of 3-substituted 2-indolymethanols have been afforded in moderate to excellent yields. This strategy has the advantage of short reaction time, wide substrate scope, mild reaction conditions, and so on. The synthetic utility was further demonstrated by gram-scale reaction and derivatization of the desired product.

In order to find new compounds with high activity, 20 1,2,3-benzotriazin-4-one thioether (sulfone) derivatives containing oxadiazole fragments were designed and synthesized. The results of in vitro antibacterial activity assay showed that 6-chloro-3-(5-ethylsulfonyl)-1,3,4-oxadiazo-2-ylmethyl)benzo[d][1,2,3]triazin-4(3H)-one (7c) had a good inhibitory effect on Sclerotinia sclerotiorum with an EC₅₀ value of 3.84 mg/L, which was comparable to that of the control agent hymexazol (5.43 mg/L). The toxicity of 7c (1.81 mg/L) against Rhizoctonia solani was comparable to that of carbendazim (1.09 mg/L), and significantly higher than that of the control agent hymexazol (45.70 mg/L). At the concentrations of 100 and 200 mg/L, the protective effects of compound 7c against Rhizoctonia solani were 78.51% and 84.48%, and the curative effects of compound 7c were 60.34% and 78.91%, respectively. At low concentrations, the curative effect was comparable to that of carbendazim (61.53%). At a concentration of 100 mg/L, some compounds had certain in vitro activities against Caenorhabditis elegans and Bursaphelenchus xylophilus, and the LC₅₀ value of 3-(5-ethylthio)-1,3,4-oxadiazo-2-ylmethyl)benzo[d][1,2,3]triazin-4(3H)one (6a) against C. elegans was 3.96 mg/L, which was better than that of fosthiazate (57.39 mg/L) and comparable to that of fluopyram (4.68 mg/L). However, the virulence of compound 6a (50.28 mg/L) against B. xylophilus was lower than that of fosthiazate (24.68 mg/L) and fluopyram (0.57 mg/L). The target compounds synthesized have high fungicidal activity and certain nematicidal activity, which can provide a reference for the study of new 1,2,3-benzotriazine-4-one derivatives.

A Pd-catalyzed electrophilic-electrophilic reductive cross-coupling of allylic esters with aryl iodides involving the insertion of SO₂ has been reported. This reaction employs manganese powder as reductant, cheap and readily available sodium metabisulfite as SO₂ substitute, and features good reactivity, high rselectivity and broad substrate scope.

Transition-metal catalyzed cross-coupling is one of the basic strategies for the C—C bond formation. However, it is difficult to achieve satisfactory results when terminal alkynes with electron-withdrawing group such as propiolate esters are used. The reason behind this might be the easy polymerization of this type of alkynes in the presence of base. A tetrahydroxydiboron and copper sulfate co-promoted cross-coupling/cyclization of propiolate esters and o-iodobenzoic acid for the facile and efficient construction of phthalides is described. Preliminary mechanism study indicates that tetrahydroxydiboron can inhibit the polymerization of propiolate esters and increase the reaction rate. This method is characterized by high regio- and stereoselectivities, mild reaction conditions, short reaction time, broad substrate scope, and excellent functional group compatibility.

Adenosine triphosphate (ATP)-citrate lyase (ACLY) converts cytosolic citrate from the tricarboxylic acid cycle (TCA cycle) into acetyl coenzyme A (acetyl-CoA), which is a building block for cholesterol and fatty acid synthesis. Abnormally high expression of ACLY is associated with multiple metabolic diseases including dyslipidemia, atherosclerosis and non-alcoholic steatohepatitis (NASH), making ACLY an appealing target. In previous work, 326Eb was discovered, featuring an alkenyl dicarboxylic acid scaffold as a novel ACLY inhibitor. 326E can be potentially used to treat hypercholesterolemia and is currently undergoing phase II clinical trials. In this study, a series of diacids containing conjugated diene were developed based on impurities in manufacturing process of 326E in good manufacturing practice of medical products (GMP) condition, which represented a unique structural type different from known ACLY inhibitors. Among synthesized all eight possible isomers, compounds 43ZZ and 52EE exhibited significant inhibitory effect on de novo lipogenesis and gluconeogenesis in vitro and 43ZZ showed favorable pharmacokinetics. Furthermore, oral administration of 43ZZ and 52EE demonstrated a marked reduction of hepatic lipogenesis, along with lowered plasma levels of triglyceride and cholesterol, thereby confirming that these diene diacids as novel ACLY inhibitors have therapeutic potential for hyperlipidemia.

An efficient approach to access 1-substituted-amino-2-arylvinyl 1H-indole-1-carboxylates was achieved through calcium trifluoromethanesulfonimide [Ca(NTf₂)₂] catalyzed addition process of ynamides with tert-butyl 1-indolecarboxylate. After verification with 15 substrates, the yields of this method were stable between 52% and 87%, and regioselectivities were excellent.