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Iron-Mediated Regioselective C–H Chalcogenation of Tyrosine Derivatives Using Mechanochemistry 铁介导的区域选择性C-H加硫酪氨酸衍生物的机械化学反应
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.joc.5c03001
Zihan Yu, Junlong Li, Wuga Jiala, Kui Yang, Qiqi Song, Zheyu Li, Wenbo Ma
An iron-mediated direct chalcogenation of tyrosine-containing peptides has been developed. This protocol operates under mechanochemical conditions and exhibits broad functional group tolerance. Furthermore, the synthetic utility of this protocol was demonstrated by the late-stage functionalization of pharmaceutical compounds. Preliminary mechanistic studies indicated that a radical pathway is likely to be operative.
一种铁介导的含酪氨酸肽的直接加硫反应已经被开发出来。该方案在机械化学条件下运行,并表现出广泛的官能团耐受性。此外,该方案的合成效用是由药物化合物的后期功能化证明。初步的机制研究表明,一个激进的途径可能是有效的。
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引用次数: 0
KHMDS-Mediated Direct Heteroarylation of C(sp3)-H Bonds of 9,10-Dihydroacridines and Analogues for Discovery of Potent Antimicrobial Agents. kmds介导的9,10-二氢吖啶烷及其类似物C(sp3)-H键的直接异芳基化,用于发现有效的抗菌剂。
IF 3.6 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.joc.5c02855
Taiyou Xu, Wanqiu Peng, Luhang Yang, Ya Hong, Xingxing Wu

Acridine scaffolds are key pharmacophores in bioactive molecules and functional materials that exhibit diverse biological activities. Although C9-functionalization methods of 9,10-dihydroacridines have advanced, the development of efficient and transition-metal-free strategies for direct heteroarylation of sp3 C-H bonds to access structurally diverse acridines is highly demanding. Herein, we report a KHMDS-mediated direct coupling of 9,10-dihydroacridines with readily available heteroaryl halides under mild and simple conditions. This approach enables rapid and modular access to 9-heteroaryl dihydroacridine derivatives. The resulting functionalized products can be readily transformed into a diverse set of (hetero)aryl-substituted acridinium salts, which shall inspire future applications in the design of photocatalysts and fluorescent dyes. Biological tests demonstrated potent and wide-ranging antifungal activity, underscoring the potential of these products as fungicide leads for agrochemical development.

吖啶支架是生物活性分子和功能材料中重要的药效载体,具有多种生物活性。虽然9,10-二氢吖啶烷的c9功能化方法已经取得了进展,但开发高效且无过渡金属的sp3 C-H键直接杂芳化策略以获得结构多样化的吖啶烷的要求很高。在此,我们报道了在温和和简单的条件下,khmds介导的9,10-二氢吖啶和容易获得的杂芳基卤化物的直接偶联。这种方法可以快速和模块化地获得9-杂芳基二氢吖啶衍生物。由此产生的功能化产物可以很容易地转化为各种(杂)芳基取代吖啶盐,这将激发未来在光催化剂和荧光染料设计中的应用。生物试验显示了有效和广泛的抗真菌活性,强调了这些产品作为农药开发杀菌剂的潜力。
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引用次数: 0
Visible Light-Mediated [3 + 2] Cycloadditions of Vinylcyclopropanes with Alkenes/Alkynes Using CBr4 and an Organic Photocatalyst 用CBr4和有机光催化剂催化乙烯基环丙烷与烯/炔的[3 + 2]环加成反应
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.joc.5c02490
Yi Sun, Yanting Yang, Xiaobing Huang, Lin Yuan, Qiang Bian, Jun Ren, Zhongwen Wang
Utilizing a readily available and highly efficient organic photocatalyst (QXPT-NPy, 0.5 mol %) and inexpensive CBr4 (0.5 mol %) as a bromine radical precursor, the [3 + 2] cycloadditions of vinylcyclopropanes with alkenes/alkynes were successfully achieved under irradiation of 420 nm blue LEDs. A broad scope of alkenes and alkynes participated efficiently in the reaction, and structurally diverse cyclopentane and cyclopentene derivatives were afforded in up to 97% yield and 95:5 dr.
利用一种易于获得的高效有机光催化剂(QXPT-NPy, 0.5 mol %)和廉价的CBr4 (0.5 mol %)作为溴自由基前驱体,在420 nm蓝光led的照射下成功地实现了乙烯基环丙烷与烯烃/炔的[3 + 2]环加成反应。广泛的烯烃和炔烃有效地参与了该反应,并得到了结构多样的环戊烷和环戊烯衍生物,收率高达97%,dr为95:5。
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引用次数: 0
Homologative Enamination of Aromatic Aldehydes as a Route to β-Dialkylaminostyrenes 芳香醛的同源漆化制备β-二烷基氨基苯乙烯的途径
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.joc.5c03028
Anastasia A. Smorodina,Mariia S. Iugova,Evgeny M. Buev,Taisiya I. Ichetovkina,Vladimir S. Moshkin,Vyacheslav Y. Sosnovskikh
Enamines serve as pivotal compounds in synthetic organic chemistry. Herein, a homologative enamination of aromatic aldehydes was achieved through three steps: [3 + 2] cycloaddition with nonstabilized azomethine ylide, quaternization with various alkyl halides, and eliminative ring-cleavage of oxazolidine core with sodium hydride in dimethyl sulfoxide. The obtained dialkylstyrylamines were employed as useful intermediates, furnishing a number of phenethylamines via reduction with sodium borohydride in good yields or were acylated with trifluoroacetic anhydride. We also demonstrated that the titled enamination could be performed in two step manner applying thermal ring-cleavage of 5-aryloxazolidine with trifluoroacetic anhydride, providing N-acylaminostyrenes in moderate yields. The proposed methodology for the homologative enamination features with gram-scale approach, readily available inexpensive materials, and simple laboratory techniques.
胺类化合物是合成有机化学中的关键化合物。本文通过与非稳定亚甲酰亚胺进行[3 + 2]环加成,与各种卤代烷基进行季铵化反应,以及在二甲亚砜中与氢化钠进行恶唑烷核的消环裂解,实现了芳香醛的同源化釉化反应。所得到的二烷基苯基胺被用作有用的中间体,通过硼氢化钠还原,收率很高,或用三氟乙酸酐酰化。我们还证明了用三氟乙酸酐热裂解5-芳基恶唑烷,可以用两步的方式进行标题化,以中等收率得到n -酰基氨基苯乙烯。该方法具有克级方法、容易获得的廉价材料和简单的实验室技术。
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引用次数: 0
Iridium-Catalyzed Desymmetric Hydroalkynylation of Cyclopentenes to Construct 1,3-Stereocenters 铱催化环戊烯的不对称氢炔基化合成1,3-立体中心
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.joc.5c02755
Tong Wan, En-Ze Lin, Huanrong Li, Bi-Jie Li
Transition metal-catalyzed enantioselective alkene hydroalkynylation to construct a nonadjacent stereocenter, especially in cyclic systems, remains underexplored. Herein, we report an iridium-catalyzed enantioselective hydroalkynylation of cyclopentene substrates containing an amide as the directing group, affording cyclopentanes with nonadjacent 1,3-stereocenters with high regio-, diastereo-, and enantioselectivity. The alkynyl group in the product enables further transformations, providing a reliable route to enantioenriched cyclic compounds with nonadjacent stereocenters.
过渡金属催化的对映选择性烯烃氢烷基化以构建非相邻的立体中心,特别是在环体系中,仍未得到充分的研究。本文中,我们报道了一种铱催化的环戊烯底物的对映选择性氢烷基化反应,该反应以酰胺为导向基团,得到具有非相邻1,3立体中心的环戊烷,具有高的区域选择性、非对映性和对映选择性。产物中的炔基使进一步的转化,提供了一个可靠的途径,以非相邻的立体中心富集对映体环化合物。
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引用次数: 0
BODIPYS in Multicomponent Reactions. Synthesis of BODIPY-4H-Pyran Hybrids 多组分反应中的BODIPYS。BODIPY-4H-Pyran杂化物的合成
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.joc.5c02560
Alexis S. Zamora-Vázquez, Diana E. Ramírez-Ornelas, Enrique Alvarado-Martínez, Fernando Hernández, Miguel A. Vázquez, Eduardo Peña-Cabrera
The Liebeskind-Srogl (LSCC) and Suzuki cross-coupling reactions were employed to prepare 10 formyl-substituted BODIPY dyes in high yields (64–98%). These derivatives were reacted with malononitrile, ethyl acetoacetate and ammonium hydroxide in a multicomponent reaction (MCR) to furnish highly substituted 4H-pyranes. In Method A, conventional heating was employed to prepare nine such derivatives in yields that range from 25 to 72%. In Method B, six derivatives were prepared under ultrasound-activation in 35–64% isolated yields and reduced reaction times. The photophysical properties of the 4H-pyranes thus prepared were measured. A rather low fluorescence quantum yield (ΦF = 0.61–5.67%) of the products was observed. Moreover, absorption and emission are in accordance with typical for BODIPY green-yellow region. Finally, it was observed excellent chromophore behavior (log εmax = 3.94–4.91 M–1 cm–1) and moderate Stokes shift values for the product series (599–728 cm–1), and finally 2,3,5,6-tetraarylBODIPY product with absorption and emission displaced to red (627 and 718 nm, respectively).
采用Liebeskind-Srogl (LSCC)和Suzuki交叉偶联反应制备了10种甲酰取代的BODIPY染料,收率高达64-98%。这些衍生物与丙二腈、乙酰乙酸乙酯和氢氧化铵在多组分反应(MCR)中反应得到高取代的4h -吡喃。在方法A中,采用常规加热方法制备了9种此类衍生物,收率从25%到72%不等。方法B在超声活化下制备了6个衍生物,分离率为35-64%,缩短了反应时间。测定了所制备的4h -吡喃的光物理性质。产物的荧光量子产率较低(ΦF = 0.61-5.67%)。吸收和发射符合典型的BODIPY黄绿色区域。最后,该产物具有良好的发色团行为(log εmax = 3.94 ~ 4.91 M-1 cm-1)和适度的Stokes位移值(599 ~ 728 cm-1),最终,2,3,5,6- tetraarylbodipy产物的吸收和发射位移分别为627 nm和718 nm)。
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引用次数: 0
DBU-Promoted Cascade Synthesis of Dihydrocoumarins from p-Quinone Methides and o-Hydroxy Aldimines dbu促进对醌和邻羟基醛胺级联合成二氢香豆素的研究
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-02 DOI: 10.1021/acs.joc.5c02600
Yingpeng Su,Qinqin Ling,Caixia Yang,Zhengang Han,Haiyang He,Shufang Zhang,Jinjin Chang,Xiaolong Zhao,Congde Huo,Xiaolei Wang
A facile synthesis of dihydrocoumarin derivatives has been successfully accessed with ortho-hydroxyphenyl-substituted para-quinone methides (p-QMs) and ortho-hydroxy aromatic aldimines. The reaction proceeds through a Michael addition followed by an intramolecular phenolysis sequence. This cascade strategy provides structurally diverse 4-aryl-3,4-dihydrocoumarins in good to excellent yields with excellent diastereoselectivity. Moreover, this versatile method exhibits significant promise for the synthesis of natural products and biologically relevant compounds that possess a substituted coumarin skeleton.
以邻羟基苯基取代对苯二酚和邻羟基芳醛胺为原料,成功地合成了二氢香豆素衍生物。反应通过迈克尔加成进行,然后是分子内酚解序列。这种级联策略提供了结构多样的4-芳基-3,4-二氢香豆素,收率高,非对映选择性好。此外,这种多用途的方法在合成具有取代香豆素骨架的天然产物和生物相关化合物方面具有重要的前景。
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引用次数: 0
Synthesis of Six-Membered Ring Nucleoside Analogues through the Palladium-Catalyzed Tandem Allylic Substitution Reaction 钯催化串联烯丙基取代反应合成六元环核苷类似物
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-02 DOI: 10.1021/acs.joc.5c02941
Ke-Xin Huang,Ke-Xin Zhang,Cai-Jing Li,Ji-Ling Tan,Chang-Yin Li,Zhao-Yang Chen,Xue-Guo Liu
We have developed an efficient Pd-catalyzed tandem allylic substitution reaction for the synthesis of six-membered ring nucleoside analogues. This strategy employs α-purine-substituted acetophenones (α-purine-substituted acetone) as challenging dinucleophiles, which react with 2-methylenepropane-1,3-diyl diacetate to afford the corresponding products in high yields (up to 91%) across a broad range of substrates (21 examples). The use of commercially available catalysts, a broad substrate scope, and the potential application value of the products make this approach highly attractive and pioneering in the field.
我们开发了一种高效的pd催化串联烯丙基取代反应,用于合成六元环核苷类似物。该策略采用α-嘌呤取代的苯乙酮(α-嘌呤取代的丙酮)作为具有挑战性的亲核试剂,与2-亚甲基丙烷-1,3-二乙酸二酯反应,在广泛的底物中以高收率(高达91%)提供相应的产物(21个例子)。商业上可用的催化剂的使用,广泛的衬底范围,以及产品的潜在应用价值使这种方法在该领域具有很高的吸引力和开创性。
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引用次数: 0
Dichloromethane as a Carbon Source for the Base Promoted Synthesis of Methylene-Bridged Bis-Enaminones and Bis-Pyrazoles 以二氯甲烷为碳源碱催化合成亚甲基桥联双胺酮和双吡唑
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-02 DOI: 10.1021/acs.joc.5c02633
Wanting Liang,Jingyan Liu,Jie-Ping Wan,Yunyun Liu
The reactions of NH-enaminones with dichloromethane (DCM) leading to the synthesis of methylene-bridged bis-enaminones have been realized under redox neutral conditions wherein the DCM acts as both the reaction medium and methylene donor. The substrates of bulk chemical DCM and easily accessible enaminones make the present method rather practical, thus enabling the efficient synthesis of methylene-bridged bis-pyrazoles via simple condensation of the methylene-bridged bis-enaminones with hydrazines under acid promotion.
在氧化还原中性条件下,以二氯甲烷(DCM)作为反应介质和亚甲基给体,实现了nh -胺酮与二氯甲烷(DCM)合成亚甲桥双胺酮的反应。由于本体化学DCM的底物和容易获得的胺酮使得本方法非常实用,因此在酸促进下,通过亚甲基桥接双胺酮与肼的简单缩合,可以高效合成亚甲基桥接双吡唑。
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引用次数: 0
One-Step Deoxygenated Oxidative C–N Coupling of Azine N-Oxides with Alicyclic Amines via Copper(I) Catalyst-dppf Cooperation 铜(I)催化剂-dppf配合作用下Azine n -氧化物与脂环胺一步脱氧氧化C-N偶联
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-02 DOI: 10.1021/acs.joc.5c02699
Yanrui Wang,Weiqi Zhu,Jiangbin Yang,Zihui Lu,Yu Ding,Jianchun Wang,Honghua Rao
Transition metal (TM)-catalyzed direct C–H amination on free and fused pyridines is challenging, while it is much easier for their N-oxide derivatives. Unfortunately, most TM-catalysis is commonly used for nondeoxyamination and often limited to specific N-oxide and amine substrates. We herein disclose a combination of a copper(I) catalyst and dppf for deoxygenated oxidative C–N coupling of azine N-oxides to realize facile aminations on their parent azines, wherein dppf plays a crucial role in the deoxygenation step in the catalytic cycle. Moreover, this protocol tolerates a wider variety of N-oxides and free alicyclic amines to promise broader application potential.
过渡金属(TM)催化游离吡啶和熔融吡啶的直接C-H胺化是具有挑战性的,而它们的n -氧化物衍生物则容易得多。不幸的是,大多数tm催化通常用于非脱氧胺化,并且通常仅限于特定的n -氧化物和胺底物。我们在此公开了一种铜(I)催化剂与dppf的组合,用于azine n -氧化物的脱氧氧化C-N偶联,以实现其母体azine上的易胺化,其中dppf在催化循环中的脱氧步骤中起关键作用。此外,该方案可耐受更广泛的n -氧化物和游离脂环胺,以保证更广泛的应用潜力。
{"title":"One-Step Deoxygenated Oxidative C–N Coupling of Azine N-Oxides with Alicyclic Amines via Copper(I) Catalyst-dppf Cooperation","authors":"Yanrui Wang,Weiqi Zhu,Jiangbin Yang,Zihui Lu,Yu Ding,Jianchun Wang,Honghua Rao","doi":"10.1021/acs.joc.5c02699","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02699","url":null,"abstract":"Transition metal (TM)-catalyzed direct C–H amination on free and fused pyridines is challenging, while it is much easier for their N-oxide derivatives. Unfortunately, most TM-catalysis is commonly used for nondeoxyamination and often limited to specific N-oxide and amine substrates. We herein disclose a combination of a copper(I) catalyst and dppf for deoxygenated oxidative C–N coupling of azine N-oxides to realize facile aminations on their parent azines, wherein dppf plays a crucial role in the deoxygenation step in the catalytic cycle. Moreover, this protocol tolerates a wider variety of N-oxides and free alicyclic amines to promise broader application potential.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Journal of Organic Chemistry
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