Metal-free nucleophilic 7,8-dearomatization of quinolines:Spiroannulation of aminoquinoline protected amino acids

Atom-and step-economy in IBX assisted diversity-oriented synthesis is achieved with a versatile AQ auxiliary α-amino acid analogs offering rapid access to polycyclic spiro-quinolines featuring a quaternary stereocenter in 20%–91% yields under mild conditions via 7,8-dearomatization of quinolines. Free of a preinstalled activation group is highlight of this intramolecular oxidation spiroannulation tandem reaction. This type of N-heterospirocycles, traditionally difficult to access, may open the door to a potentially interest scaffold for synthetic and medicinal chemistry.

Anion cascade reactions Ⅲ:Synthesis of 3-isoquinuclidone bridged polycyclic lactams

Bridged polycyclic lactams are important structural units in organic functional materials,natural products,and pharmaceuticals.A flexible and efficient anion cascade reaction was developed for the preparation of bridged polycyclic lactams from readily available malonamides and 1,4‑dien-3-ones.Various highly substituted bridged polycyclic lactams were synthesized in good to excellent yields by tandem nucleophilic sequences in the presence of t BuOK in commercially available EtOH solvent at 60℃.Notably,the simple reactions can be run on a gram scale.Mechanistically,bis-Michael addition reaction and hemiaminalization reactions are involved in the tandem transformation.

正视儿童脉络膜厚度的分布特征及相关影响因素

目的:应用扫频源光学相干断层扫描血流成像技术(SS-OCTA)观察正视儿童黄斑区脉络膜厚度(CHT)的分布特征,并探讨其相关影响因素。方法:横断面研究。连续性纳入2021年5—9月在郑州大学第一附属医院眼科就诊的6~12岁正视儿童63例。以黄斑中心凹为中心,使用SS-OCTA测量黄斑区的CHT和脉络膜血管指数(CVI),根据ETDRS分区将图像划分为3个环区:黄斑中心凹区(直径0~1 mm)、内环区(直径1~3 mm)和外环区(直径3~6 mm)。均纳入右眼数据分析。采用单因素方差分析比较3个环区和内、外环区的上方、颞侧、下方和鼻侧4个区域的CHT,并采用单因素线性回归和多元线性回归分析3个环区的CHT与性别、年龄、屈光度、父母屈光度、眼轴长度、瞳孔直径和CVI等参数的相关性。结果:黄斑中心凹区、内环区和外环区的CHT分别为(320±58)(315±55)(299±47)μm(F=2.77,P=0.065),外环区的CHT比黄斑中心凹区的CHT薄(t=2.20,P=0.025),其余两两环区CHT相比,差异均无统计学意义(均P>0.05)。黄斑中心凹区和内、外环区的上方、颞侧、下方及鼻侧共9个区域的CHT相比,总体差异有统计学意义(F_(不同区域)=19.20,P<0.001),在内环区和外环区的上方、颞侧、下方和鼻侧4个区域的CHT相比,差异均有统计学意义(F_(内环区)=8.15,P<0.001;F_(外环区)=43.11,P<0.001),均是鼻侧最薄。经单因素线性回归分析,黄斑中心凹区、内环区的CHT均与瞳孔直径相关(β=14.31,P=0.035;β=13.88,P=0.039);黄斑中心凹区、内环区和外环区的CHT均与对应环区的CVI相关(β=264.60、335.87、463.22,均P<0.001)。去除混杂因素后,经多因素线性回归分析发现黄斑中心凹区、内环区和外环区的CHT均与对应环区的CVI呈正相关(β=233.96、306.93、429.25,均P<0.001),其中黄斑中心凹区、内环区的CHT与瞳孔直径呈正相关(β=18.32、17.56,P=0.023、0.027);内环区和外环区的CHT与性别有相关性(β=24.92、23.50,P=0.043、0.038);外环区的CHT与年龄呈正相关(β=10.71,P=0.025);与其余参数间无相关性。结论:6~12岁正视儿童黄斑外环区的CHT比黄斑中心凹区的薄,且内、外环区的鼻侧最薄。男性、年龄越大、瞳孔直径越大和CVI越大的儿童,黄斑各环区的CHT越厚。

Synthesis of[60]Fullerene-Fused Allylbenzofurans via Palladium-Catalyzed Migration Reaction

Chemical functionalization of fullerenes has been an important topic in fullerene chemistry. Herein, an unprecedented Pd-catalyzed migration reaction of [60]fullerene with allyloxy-tethered aryl iodides is present for the preparation of novel [60]fullerene-fused allylbenzofurans. The use of 1,2-bis(diphenylphosphino)benzene (DPPBz) as a ligand is crucial for the success of the transformation. The reaction shows high chemo- and regioselectivity, and is flexible with regard to allyl-migration site, providing a new and efficient approach to rare [60]fullerene-fused benzofurans. Control experiments disclose that the reaction most probably undergoes a sequential C—O bond cleavage/allyl-migration/intermolecular cycloaddition cascade process.

Personalized cancer vaccines from bacteria-derived outer membrane vesicles with antibody-mediated persistent uptake by dendritic cells

Nanocarriers with intrinsic immune adjuvant properties can activate the innate immune system while delivering tumor antigen,thus efficiently facilitating antitumor adaptive immunity.Bacteria-derived outer membrane vesicles(OMVs)are an excellent candidate due to their abundance of pathogen associated molecular patterns.However,during the uptake of OMVs by dendritic cells(DCs),the interaction between lipopolysaccharide and toll-like receptor 4 induces rapid DC maturation and uptake blockage,a phenomenon we refer to as“maturation-induced uptake obstruction"(MUO).Herein we decorated OMV with the DC-targeting aDEC205 antibody(OMV-DEC),which endowed the nanovaccine with an uptake mechanism termed as 4<not restricted to maturation via antibody modifying”(Normandy),thereby overcoming the MUO phenomenon.We also proved the applicability of this nanovaccine in identifying the human tumor neoantigens through rapid antigen display.In summary,this engineered OMV represents a powerful nanocarrier for personalized cancer vaccines,and this antibody modification strategy provides a reference to remodel the DC uptake pattern in nanocarrier design.

Copper（I）-Catalyzed Intramolecular N-N Coupling of Cyclopropyl O-Acyl Ketoximes： Synthesis of Spiro-fused Pyrazolin-5-ones

一条方便催化铜的途径经由 intramolecular NN 契约形成反应从容易地可得到的 cyclopropyl O 酰 ketoximes 为代替的熔化 spiro 的 pyrazolin-5-ones 的合成被开发了。这些催化反应在优秀收益继续一个宽广范围。

Understanding the Electronic Structure and Stability of B_(n)X_(n)^(0/2-)(n=4,6;X=H,F,Cl,Br,I,At,Ts)Clusters

Main observation and conclusion Borane clusters and their derivatives have attracted extensive attention in inorganic chemistry due to their fascinating multi-center bonding patterns and physicochemical properties.Here we report a systematic theoretical investigation on the geometry.

Dimethyl sulfoxide-aided copper(0)-catalyzed intramolecular decarbonylative rearrangement of N-aryl isatins leading to acridones

Described here is the first example of Cu(0)-catalyzed intramolecular decarbonylative rearrangements of readily available N-aryl isatins assisted by solvent dimethyl sulfoxide(DMSO)under air atmosphere and additive-free conditions leading to various biologically important acridones in good to excellent yields.This novel transformation is proposed to go through a sequential DMSO-aided Cu insertion into the amide C-N bond,CO extrusion,Cu migration,reductive elimination and DMSO-aided proton migration processes,involving multiple types of bond cleavage and formation in a single chemical step.

Iridium complex of porphycene:a new member of metalloporphycene

Iridium(Ⅲ)porphycene complex was synthesized and structurally characterized for the first time.The introduction of the posttransition iridium(Ⅲ)ion not only significantly enhances the absorption intensity at the end of visible region,but also displays efficient singlet oxygen quantum yield(76%),which is applicable for photodynamic therapy in living cells.