The Pfitzinger reaction has long served as a notable synthesis pathway for quinoline-4-carboxylic acids. Although recognized for its synthetic potential since its discovery >138 years ago, a truly catalytic variant has remained elusive until now. Herein, we present a novel 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG)-catalyzed Pfitzinger reaction that employs N-[(alpha-trifluoromethyl)vinyl]isatins with amines and alcohols, providing direct routes to 2-CF3-quinoline-4-carboxamides and carboxylic esters. This method is not only green and environmentally benign but also accommodates the introduction of other functional groups like CF2H and CO2Me at the C2 position of quinoline skeleton. The utility of this methodology was demonstrated by the broad substrate scope, the late-stage modification of commercial drugs, and the diverse derivatization of quinoline framework. More importantly, this work not only opens up a new avenue for the activation of amide CN bonds in catalytic reaction development, but also unlocks the huge potential of some 2-trifluoromethyl quinolines with strong inhibitory activity against PTP1B or optoelectronic application in organic light-emitting diodes. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Herein we report a novel, efficient gold-catalyzed tandem reaction of alkynols with TMSN3 as a nitrogen source to yield alkenylnitrile derivatives in the presence of TFA. The reaction proceeds under mild conditions and exhibits broad functional group tolerance. The synthetic utility of this reaction has been reflected by its applicability to a wide range of alkynol substrates.

An efficient and mild protocol for the visible light-induced radical cascade difluoromethylation/cyclization of imidazoles with unactivated alkenes using easily accessible and bench-stable difluoromethyltriphenylphosphonium bromide as the precursor of the -CF2H group has been developed to afford CF2H-substituted polycyclic imidazoles in moderate to good yields. This strategy, along with the construction of Csp3-CF2H/C-C bonds, is distinguished by mild conditions, no requirement of additives, simple operation, and wide substrate scope. In addition, the mechanistic experiments have indicated that the difluoromethyl radical pathway is essential for the methodology.

Goniomitine is of the aspidosperma alkaloid family, with an angularly fused tetracyclic skeleton housing an all-carbon quaternary carbon chiral center alongside an aminal functional group. This natural product has garnered attention as a synthetic target due to its intriguing molecular architecture and anti-proliferative activity in recent years. Following the first synthesis of (-)-goniomitine by Takano in 1991, synthetic chemists have developed various methods. This review provides an overview of the methodologies used in the synthesis of goniomitine in racemic and enantiopure forms via divergent construction indole framework, indole functionalization, and the integrated oxidation/reduction/cyclization (iORC) sequence from 1991 to 2023.

AbstractCopper‐catalyzed aryl amidation reactions have received increasing interest in recent years and have been widely applicable in the total synthesis of a diverse range of structurally complex natural products. This review covers the synthetic assembly of a wide range of natural products, with copper‐catalyzed aryl amidation being the key conversion process.

An efficient and facile strategy for the synthesis of 6-(sulfonylmethyl)phenanthridines and its derivatives has been developed via tandem sulfonylation cyclization of vinyl azides under mild conditions in the absence of any catalysts and additives. The reaction simply utilizes easily accessible and cheap K2S2O5 as the sulfur dioxide source, delivering functionalized phenanthridines in moderate to excellent yields with operational simplicity and gram-scale synthesis, as well as good functional-group tolerance.

Herein, we report a Cu-catalyzed redox isomerization-reductive deuteration sequence, providing facile access to a range of α-deuterated amino acid esters featuring an Z-configured alkene moiety with high yields. The advantages of this sequence include mild conditions, broad substrate scope, and excellent stereoselectivity. This research also represents a rare example of the Z-selective redox isomerization of propargyl amines.

The focus review discusses the synthesis of an important member of the monoterpene indole alkaloid family, mersicarpine. Biosynthetically, mersicarpine, isolated from the Kopsia fruticosa and Kopsia arborea, is proposed to share the same biogenetic pathway as melodinine E and leuconolam, and has a fused tetracyclic [6.5.6.7] ring system characterized by an unusual tetrahydro-2H-azepine ring and a hemiaminal motif. As a consequence, this intriguing structural feature has attracted considerable attention from synthetic chemists. The review focuses on the synthesis of mersicarpine from its first synthesis to the most recent one, ranging from 2008-2022.

Aurantioclavine, isolated by Kozlovskii from Penicillium aurantiovirens, is a unique member of the 3,4-disubstituted indole alkaloids distinguished by an azepino[5,4,3-cd]indole. As an essential intermediate in the biosynthesis of the complex polycyclic alkaloids of the fungal communesin, it has attracted considerable attention as a synthetic target. The development of various synthetic strategies for their application in total synthesis has been described. An overview focused on the synthesis of aurantioclavine from its first synthesis to the most recent one is present.

以2011-2020年《化学教育(中英文)》中"情境"为主题的文章为研究对象,从载文情况、载文内容以及引用情况与被引用情况等方面统计分析近十年来有关化学情境教育教学研究的趋势与存在的问题,并对教学提出以下几点建议:今后的教学应加强对情境素材的挖掘;情境的创设要遵循相关理论原则;关注国际教育动态;重视课后进行情境创设反思;注重习题的情境化等.

γ‐Lycorane, a degradation product of the Aromaticaceae alkaloid lycorine, is one of the most attractive molecules in the Aromaticaceae family. It remains a popular target for synthesis due to its pentacyclic structure, which presents a vehicle for demonstrating the utility of new synthetic strategies. Various synthetic methods have been developed by synthetic chemists since the first synthesis of γ‐lycorane by Nasuo in 1966. Thus, this review presents an overview of the literature on the ways utilized within the synthesis of γ‐lycorane in racemic and enantiopure forms via electrophilic arylation, Pd‐catalyzed C−C coupling, Bischler–Napieralski cyclization, Pictet–Spengler cyclization, photocyclization, radical cyclization, chiral pool synthesis, chiral auxiliary‐mediated synthesis, and catalytic asymmetric synthesis, ranging from 1966 to 2022.

(-)-alpha-Kainic acid, a unique group of nonproteinogenic amino acids, was first isolated from the Japanese marine alga Digenea simplex by Murakami et al. Due to its insecticidal activities and its neurophysiological activity in animals, it has attracted wide attention from pharmacists and chemists. Therefore, the synthetic strategies and methods have been developed rapidly. Combined with the strategies and methods of asymmetric synthesis, the research results reported in past decade were reviewed, including chiral pool synthesis, chiral auxiliary induced synthesis, and catalytic asymmetric synthesis.

Coumarins and 2H-pyran derivatives are among the most commonly found structural units in natural products. Therefore, the introduction of 2H-pyran moiety into the coumarin structural unit, i.e., dihydrocoumarin-fused dihydropyranones, is a potentially successful route for the identification of novel bioactive structures, and the synthesis of these structures has attracted continuing research interest. Herein, a chiral tertiary amine catalyzed [4 + 2] cyclization of 3-aroylcoumarines with benzyl 2,3-butadienoate was reported. In the presence of Kumar's 6'-(4-biphenyl)-β-iso-cinchonine, the desired dihydrocoumarin-fused dihydropyranone products could be obtained in up to 97% yield and 90% ee values.

“预测-观察-解释”教学策略(Predict-Observe-Explain,即POE)对探查学生理解科学概念、指导探究式教学有重要作用.分析高中“酸雨”课题中二氧化硫性质的教学问题、蕴含的核心素养教学价值,运用POE策略设计四个教学环节与四个阶段学习活动,通过预测、观察、解释等活动使学生认知发生冲突,进而实现学生对知识、概念与原理的自主建构.

电化学中的K(?)-E(?)关系式和φ-φ(?)关系式是分别求算原电池氧化还原反应平衡常数和氧化还原电对电极电势的重要公式.实际上,这2个公式也可以用来求解非氧化还原反应的平衡常数.以实例的形式讨论了这一思想的根据、方法,及其在求算水电离常数、弱酸或弱碱电离常数、难溶性电解质溶度积常数和配离子形成常数等方面的应用.

The first highly enantioselective construction of chiral cyclopropa[c]coumarins was described. Using commercially available (bis)cinchona alkaloid (DHQ)(2)PYR as the chiral Lewis base catalyst, together with Cs2CO3 as the achiral base, the reaction of a series of coumarin-3-carboxylate and 3-benzoyl coumarins with tert-butyl 2-bromoacetate could give rise to the corresponding cyclopropa[c]coumarins bearing three continuous chiral stereocenters in 83-93% ee and 90-97% ee, respectively. The reaction is proposed to proceed via an in situ generated ammonium ylide intermediate.

Enantioenriched fluorinated alpha- and beta-amino acids are often encountered in numerous pharmaceuticals and bioactive molecules, and also of great importance as probes in PET and NMR for studying the behavior of enzymes and for incorporation into peptides and drug candidates. Among various synthetic strategies developed, catalytic enantioselective synthesis proves to be one of the most facile and powerful protocols to construct such privileged structures. The past decade has witnessed considerable progress in the catalytic enantioselective construction of chiral fluorinated alpha- and beta-amino acid derivatives with structural diversity. In this review, we summarize these impressive achievements according to the bond-forming way of fluorinated alpha- or beta-amino acids, respectively, and underline the remaining challenges. This information would provide important guidance and some inspiration for the researchers engaged in organic fluorine and medicinal chemistry.

含sp3 C-P键化合物是一类重要的化学原料和有机合成中间体.近年来,通过过渡金属催化sp3 C-H键活化反应来构筑sp3 C-P键受到了广泛关注并取得了显著的发展.根据不同的过渡金属催化剂进行分类,对近年来过渡金属催化sp3 C-H键活化构筑sp3 C-P键反应进行了综述,并对该研究领域的局限性和未来发展前景进行总结和展望.