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Trifluoromethylation Strategies of Alcohols and Phenols 醇和酚的三氟甲基化策略
IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-15 DOI: 10.1002/ajoc.202400179
Ravi Pratap Singh, Tanay Ghoshal, Vivek Mishra

In this review, we present a comprehensive update on the latest trifluoromethylation protocols for alcohols, highlighting the significant advancements and innovative strategies in this rapidly evolving field. Given the prevalence of hydroxyl groups in pharmaceutical compounds, there is a heightened interest in synthesizing functionalized organic molecules through the −CF3 functionalization of parent alcohols. Recent developments have introduced intriguing methods such as O-trifluoromethylation, dehydroxylative trifluoromethoxylation, deoxytrifluoromethylation, and oxytrifluoromethylation of readily available alcohols. These protocols enable the efficient single-step construction of diverse structures featuring C−CF3 and C−OCF3 bonds. This review aims to encapsulate the significant progress, structural diversity, and mechanistic insights of these transformative reactions, emphasizing their substrate scope and the underlying reaction pathways that drive these advancements.

在这篇综述中,我们全面介绍了最新的醇三氟甲基化协议,重点介绍了这一快速发展领域的重大进展和创新策略。鉴于羟基在医药化合物中的普遍存在,人们对通过母体醇的 -CF3 功能化合成功能化有机分子的兴趣日益浓厚。最近的发展引入了一些有趣的方法,如 O-三氟甲基化、脱羟基三氟甲氧基化、脱氧三氟甲基化以及现成醇的氧三氟甲基化。通过这些方法,可以高效地一步构建以 C-CF3 和 C-OCF3 键为特征的各种结构。本综述旨在概括这些变革性反应的重大进展、结构多样性和机理见解,强调其底物范围和推动这些进展的基本反应途径。
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引用次数: 0
Front Cover: Total Synthesis of Eutyscoparol A and Violaceoid C (Asian J. Org. Chem. 7/2024) 封面:Eutyscoparol A 和 Violaceoid C 的全合成(《亚洲有机化学杂志》,第 7/2024 期)
IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-15 DOI: 10.1002/ajoc.202480701
Dr. Takatsugu Murata, Takuto Iwayama, Teppei Kuboki, Shotaro Taguchi, Shou Tsugawa, Takumi Yoshida, Hisazumi Tsutsui, Ayana Shimauchi, Yukiho Kosaka, Prof. Isamu Shiina

In article number e202400148, Takatsugu Murata, Isamu Shiina, and co-workers accomplished the total syntheses of eutyscoparol A and violaceoid C via violaceoid A. The synthesis is facilitated by the desymmetrization strategy. The symmetric skeleton of quinol intermediates is shown in the cover picture with a motif of star signs. As a shooting star, the molecule is desymmetrized to key intermediate and it grows up to the eutyscoparol A. In addition, eutyscoparol A is isolated from Eutypella scoparia SCBG-8 that is an endogenous bacterium in Myrtaceae plant. Therefore, Myrtaceae plant is also seen in the cover picture.

在编号为 e202400148 的文章中,Takatsugu Murata、Isamu Shiina 及其合作者通过类中提琴酸 A 完成了 eutyscoparol A 和 violaceoid C 的全合成。喹啉中间体的对称骨架如封面图片中的星号图案所示。此外,从桃金娘科植物中的内源细菌 Eutypella scoparia SCBG-8 中分离出了 eutyscoparol A。因此,在封面图片中也可以看到桃金娘科植物。
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引用次数: 0
Approach to Spirocyclohexadienes via Visible Light‐Mediated ipso‐Cyclization of Amino Acid Derivatives with N‐(2‐Phenyl)benzoyl Groups 通过可见光介导的 N-(2-苯基)苯甲酰基氨基酸衍生物异环生成螺环己二烯的方法
IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-01 DOI: 10.1002/ajoc.202400140

Spirocycles are important structural motifs, found in natural and pharmaceutical compounds, which have attracted considerable interest in modern drug discovery research. Herein, we describe the development of a visible light‐mediated ipso‐cyclization of amino acid derivatives with N‐(2‐phenyl)benzoyl groups, allowing easy access to a variety of spirocyclohexadienes. The addition of water was found to be beneficial in promoting the reaction progress. Investigation of the substrate scope revealed that incorporating an electron‐donating moiety at the 3′‐position of the biphenyl group resulted in a more favorable outcome for spirocycle formation.

螺环是天然化合物和药物化合物中的重要结构基团,在现代药物发现研究中引起了极大的兴趣。在此,我们介绍了在可见光介导下,对带有 N-(2-苯基)苯甲酰基的氨基酸衍生物进行同环化的方法,从而轻松获得各种螺环己二烯。研究发现,加水有利于促进反应的进行。对底物范围的研究表明,在联苯基团的 3'- 位上加入一个电子供体,对螺环的形成更为有利。
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引用次数: 0
Construction of Polymers with Highly Dispersed Reactive Phases and Open Pores for Catalyzing the Efficient Synthesis of CO2 to α‐Methylene Cyclic Carbonates 构建具有高度分散活性相和开放孔隙的聚合物,用于催化 CO2 与 α-亚甲基环碳酸盐的高效合成
IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-01 DOI: 10.1002/ajoc.202400087

Selective capture of carbon dioxide as a C1 feedstock for the preparation of high‐value chemicals has been recognised as an important way to mitigate the crisis. In this work, a new heterogeneous catalyst, Cu@CP‐PII, was developed through the rational construction of an open‐pore organic skeleton, which is easy to synthesise and highly efficient. With the synergistic effect between the high CO2 affinity of the porous skeleton and the highly dispersed Cu(I) sites of the activated alkynes, it can be used for the efficient preparation of α‐methylene cyclic carbonates at ambient temperature and pressure. The structure and morphology were exhaustively characterised by Solid State 13C‐NMR, FT‐IR, XPS, TEM and N2 adsorption‐desorption tests, and this catalyst possessed a high surface area of 273.7 m2 ⋅ g−1 and uniformly dispersion of CuI. To test its catalytic activity, Cu@CP‐PII in an amount of only 0.4 mol% was used as a catalyst for the carboxylative cyclization reaction of propargylic alcohols with CO2, which resulted in substrate conversions up to 100 % and yields greater than 99 %. In addition, controlled experiments and mechanistic elucidation confirmed that anhydrous and low temperatures are necessary to achieve high selective control of the target product α‐methylene cyclic carbonates.

选择性捕获二氧化碳作为制备高价值化学品的 C1 原料已被视为缓解危机的重要途径。在这项工作中,通过合理构建开孔有机骨架,开发出了一种新型异相催化剂 Cu@CP-PII,该催化剂易于合成且高效。通过多孔骨架的高二氧化碳亲和性与活化炔烃的高分散 Cu(I)位点之间的协同效应,该催化剂可用于在常温常压下高效制备α-亚甲基环碳酸盐。固态 13C-NMR、傅立叶变换红外光谱、XPS、TEM 和 N2 吸附-解吸试验对该催化剂的结构和形态进行了详尽的表征,该催化剂具有 273.7 平方米⸳g-1 的高比表面积和均匀分散的 CuI。为了测试其催化活性,研究人员将仅为 0.4 摩尔%的 Cu@CP-PII 用作催化剂,用于丙炔醇与 CO2 的羧基环化反应,结果底物转化率高达 100%,产率大于 99%。此外,对照实验和机理阐释证实,要实现对目标产物 α-亚甲基环碳酸盐的高选择性控制,必须在无水和低温条件下进行。
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引用次数: 0
Methyl‐ and Methoxy‐substituted 2‐(Pyridin‐2‐yl)‐4‐(4‐aminophenyl)quinazolines: Synthesis and Photophysical Properties 甲基和甲氧基取代的 2-(吡啶-2-基)-4-(4-氨基苯基)喹唑啉:合成与光物理性质
IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-01 DOI: 10.1002/ajoc.202400135

A series of novel 2‐(2‐pyridyl)quinazoline luminophores containing a donor aryl fragment at position 4 and methyl or methoxy groups at benzene ring has been synthesized by efficient three‐step route. The linear optical properties have been studied by UV/Vis absorption and photoluminescence spectra in two solvents. We revealed that introduction of additional methyl group or the replacement of methyl substituents with methoxy ones lead to sequentially shift of absorption and emission maximum to blue region. 9H‐Carbazol‐9‐yl‐containing derivative is characterized by hypsochromically shifted absorption band compared to its NEt2 and NPh2 counterparts. Unlike 9H‐carbazol‐9‐yl‐derivative, Et2N‐ and Ph2N‐bearing quinazolines demonstrate considerable decrease in quantum yield values when going from toluene to MeCN. Solvatochromic properties have been explored, the pronounced bathochromic shift was observed in fluorescence spectra with the increase of solvents polarity. Moreover, the compounds show significant shift of emission band with the increase of water fraction in DMSO/H2O mixture. Two‐photon optical properties have been also studied, the two‐photon absorption cross‐sections in MeCN and toluene reached 120 GM and 210 GM, respectively. The presence of additional methyl group has little impact on δTPA value, while introduction of methoxy substituents dramatically decreases TPA cross sections. Additionally, a quantumchemical calculations of synthesized compounds were performed to support the experimental data.

通过高效的三步法合成了一系列 2-(2-吡啶基)喹唑啉发光体,其第 4 位含有供体芳基片段,苯环上含有甲基或甲氧基。在两种溶剂中通过紫外/可见吸收光谱和光致发光光谱对其线性光学特性进行了研究。我们发现,引入额外的甲基或用甲氧基取代甲基取代基会导致吸收和发射最大值依次转移到蓝色区域。与 NEt2 和 NPh2 对应衍生物相比,含 9H-咔唑-9-基的衍生物的吸收带具有低色移的特点。与 9H-咔唑-9-基衍生物不同,当从甲苯转移到 MeCN 时,Et2N- 和 Ph2N-喹唑啉的量子产率值会有相当大的下降。对溶解变色特性进行了研究,发现随着溶剂极性的增加,荧光光谱会发生明显的溶解变色偏移。此外,随着 DMSO/H2O 混合物中水含量的增加,化合物的发射带也发生了明显的移动。还研究了双光子光学特性,在 MeCN 和甲苯中的双光子吸收截面分别达到 120 GM 和 210 GM。额外甲基的存在对δTPA 的影响很小,而甲氧基取代基的引入会显著降低 TPA 的截面。此外,还对合成的化合物进行了量子化学计算,以支持实验数据。
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引用次数: 0
Recent Advances in Denitrogenative Organic Transformations of 1,2,3‐Benzotriazin‐4(3H)‐ones 1,2,3-苯并三嗪-4(3H)-酮变性有机转化的最新进展
IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-01 DOI: 10.1002/ajoc.202400127

Denitrogenative organic transformations and related reactions are a class of significant approaches for carrying out unusual C−C/C‐heteroatom (C−O, C−N, C−S) bond‐forming reactions that are usually promoted by Ru, Ir, Pd, Ni, and Cu metal catalysts. In this trait, numerous methods were adopted to synthesize several pharmaceutically valuable N‐ and O‐containing heteroaromatics using 1,2,3‐benzotriazin‐4(3H)‐one as an electrophilic coupling partner. This review involves the recent achievements related to the metal/organo‐catalyzed thermal and visible‐light mediated denitrogenative approaches with 1,2,3‐benzotriazin‐4(3H)‐ones towards the synthesis of imperative N‐heteroaromatic compounds. In addition, metal and oxidant‐free ortho‐functionalization of benzotriazinones by using suitable nucleophilic partners have been discussed. In particular, the most novel methods employing Ni and Pd metal catalysts that have emerged are exhibited. Specific attention has been paid to offering the detailed mechanistic pathway to explain the role of metal catalysts and the mechanism in the absence of metal catalysts in the denitrogenative reactions under a thermal/visible light medium.

变氮有机转化及相关反应是进行不寻常的 C-C/C-杂原子(C-O、C-N、C-S)成键反应的一类重要方法,通常由 Ru、Ir、Pd、Ni 和 Cu 金属催化剂促进。在这一特性中,采用了多种方法,以 1,2,3-苯并三嗪-4(3H)-酮为亲电偶联剂,合成了多种具有药用价值的含 N 和 O 的杂芳香族化合物。本综述介绍了最近在 1,2,3-苯并三嗪-4(3H)-酮的金属/有机物催化热和可见光介导的脱氮方法方面取得的成就,这些方法用于合成必需的 N-杂芳香族化合物。此外,还讨论了利用合适的亲核伙伴对苯并三嗪酮进行无金属和无氧化剂的正官能化。特别是展示了采用镍和钯金属催化剂的最新颖方法。还特别注意提供详细的机理途径,以解释金属催化剂的作用,以及在热/可见光介质下没有金属催化剂的脱氮反应机理。
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引用次数: 0
Methanesulfonic Acid‐Catalyzed Friedel‐Crafts Alkylation: Towards Sustainable Synthesis of Arylalkanes from Donor–Acceptor Cyclopropane Ketones 甲磺酸催化的 Friedel-Crafts 烷基化反应:从供体-受体环丙烷酮实现芳基烷烃的可持续合成
IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-01 DOI: 10.1002/ajoc.202400116

We present herein Brønsted acid‐catalyzed Friedel‐Crafts alkylation of phenols with Donor–Acceptor cyclopropane ketones. The presence of the 1,4‐diphenyl butan‐1‐one and 1,3‐diphenyl propane‐1‐one motifs in various naturally occurring biologically significant molecules inspired us to pursue the direct synthesis of these structural frameworks. Utilizing methanesulfonic acid (MeSO3H) as a catalyst, we achieved a more environmentally friendly and high‐yielding synthesis, owing to its cost‐effectiveness, biodegradability, transition–metal and additives free conditions. Furthermore, we have successfully extended our developed methodology to thiophenols, resulting in the production of sulfur–based butan‐1‐one derivatives in good yields.

我们在此介绍布氏酸催化的苯酚与供体-受体环丙烷酮的 Friedel-Crafts 烷基化反应。在各种天然生物分子中存在的 1,4-二苯基丁-1-酮和 1,3-二苯基丙-1-酮基团激发了我们追求这些结构框架的直接合成。利用甲磺酸(MeSO3H)作为催化剂,我们实现了一种更环保、更高产的合成方法,这得益于其成本效益、生物降解性、不含过渡金属和添加剂的条件。此外,我们还成功地将所开发的方法扩展到了噻吩酚,从而以良好的产率生产出了硫基丁-1-酮衍生物。
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引用次数: 0
Selective Hydrogenation of Unsaturated Vinyl Ethers in Two‐Chamber Gauge‐Reactor 双室规整反应器中不饱和乙烯基醚的选择性氢化反应
IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-01 DOI: 10.1002/ajoc.202400147

A pressure gauge was incorporated into a two‐chamber glass H‐tube to continuously monitor the pressure inside a reactor when working with gases. The ex situ generated H2, D2, acetylene and CO2 were tested in pressure gauge reactors, and calibration curves were plotted. A series of unsaturated compounds with two or more double C=C bonds accessible for hydrogenation were synthesized for hydrogenation. The hydrogenation proceeded well due to constant pressure control, and the desired products were isolated in good yields. The same hydrogenation procedures were then carried out using steel autoclaves to verify the results and compare them. Surprisingly, almost the same results were obtained, confirming the effectiveness of self‐made glass reactors. The hydrogenation mechanism was further investigated using D‐labeled reagents. The kinetics of hydrogenation was studied both in manometric glass reactors and in steel autoclaves, which showed a similar nature of the main process in both reaction units. Thus, the created reactors can be effectively used in barometric transformations instead of steel autoclaves in appropriate cases.

在双室玻璃 H 型管中安装了压力表,以便在使用气体时持续监测反应器内的压力。在压力表反应器中测试了原位生成的 H2、D2、乙炔和 CO2,并绘制了校准曲线。合成了一系列具有两个或两个以上可用于氢化的双 C=C 键的不饱和化合物用于氢化。由于采用了恒压控制,氢化过程进展顺利,并以良好的产率分离出了所需的产物。然后使用钢高压锅进行了相同的氢化过程,以验证和比较结果。令人惊讶的是,结果几乎相同,这证实了自制玻璃反应器的有效性。使用 D 标记试剂进一步研究了氢化机理。在人压玻璃反应器和钢高压釜中都对氢化动力学进行了研究,结果表明两个反应单元的主要过程性质相似。因此,在适当的情况下,所制造的反应器可以有效地用于气压转化,而不是钢制高压釜。
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引用次数: 0
An Efficient Synthesis of α‐Sulfonamide Phosphonates through Metal‐Free Three‐Component Reaction 通过无金属三组分反应高效合成α-磺酰胺膦酸盐
IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-01 DOI: 10.1002/ajoc.202400100

A metal‐free three‐component reaction for the direct synthesis of α‐sulfonamide phosphonates involving sulfonamide derivatives, benzaldehyde derivatives, and diethyl phosphite, has been achieved with high yields using ethanol as a green solvent. This efficient method reduces reaction time and minimizes the use of excess reagents. Hitherto, no reports have been found in the literature for the direct synthesis of α‐sulfonamide phosphonates from the readily available aldehydes, diethyl phosphite, and sulfonamides, emphasizing the novelty and significance of this work.

以乙醇为绿色溶剂,利用磺酰胺衍生物、苯甲醛衍生物和亚磷酸二乙酯直接合成α-磺酰胺膦酸盐的无金属三组分反应实现了高产率。这种高效的方法缩短了反应时间,并最大限度地减少了过量试剂的使用。迄今为止,文献中还没有发现用现成的醛、亚磷酸二乙酯和磺酰胺直接合成α-磺酰胺膦酸盐的报道,这突出了这项工作的新颖性和重要性。
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引用次数: 0
Synthesis of Azahelicenes via Friedel‐Crafts‐Type Ring‐Closing Reaction of Axially Chiral Compounds 通过轴向手性化合物的 Friedel-Crafts 型闭环反应合成氮杂环烯
IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-01 DOI: 10.1002/ajoc.202400128

Aza[6]helicene and aza[7]helicene were synthesized by Fridel‐Crafts‐type cyclization of axially chiral compounds. From the axially chiral compounds prepared by Fischer indole synthesis, aza[6]helicene and aza[7]helicene were synthesized. Aza[7]helicene was also synthesized from an axially chiral pyrrole compound prepared by Piloty‐Robinson‐type pyrrole synthesis through simultaneous cyclization on both sides of the pyrrole ring. Aza[6]helicene isomerized readily at room temperature, while aza[7]helicene isomerization at room temperature was less likely to proceed. The cell growth inhibitory activity of each enantiomer of N‐Me‐aza[7]helicene in HeLa cells was examined. Differences in the strength of activity between the enantiomers were observed.

通过对轴向手性化合物进行 Fridel-Crafts 型环化,合成了氮杂[6]螺旋烯和氮杂[7]螺旋烯。从费舍尔吲哚合成法制备的轴手性化合物中合成出了氮杂[6]螺旋烯和氮杂[7]螺旋烯。此外,还利用 Piloty-Robinson 型吡咯合成法制备的轴手性吡咯化合物,通过吡咯环两侧的同时环化合成了氮杂[7]螺旋烯。氮杂[6]螺旋烯在室温下很容易异构化,而氮杂[7]螺旋烯在室温下异构化的可能性较小。研究了 N-Me-aza[7]helicene对映体在 HeLa 细胞中的细胞生长抑制活性。观察到对映体之间的活性强度存在差异。
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引用次数: 0
期刊
Asian Journal of Organic Chemistry
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