Journal of Organic Chemistry最新文献_第3页

Formal Synthesis of HIF-2α Inhibitor Casdatifan (AB521): Stereospecific Copper(I)-Mediated Ring Opening of Chiral 2-Aryl-cyclopropane-1,1-dicarboxylate with Aryl Grignard Reagents HIF-2α抑制剂Casdatifan （AB521）的正式合成：用芳基格氏试剂介导手性2-芳基环丙烷-1,1-二羧酸酯的立体特异性铜(I)开环

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-06 Epub Date: 2026-10-23 DOI: 10.1021/acs.joc.6c01249

Haobo Pang, Xiaopeng Yin, Zhiguo Jake Song, Michael T. Corbett, Bing Zhang, Jing Zhao

引用次数: 0

Photoinduced Selective Cyclization Cascades of Unactivated N-alkene-Linked Indoles with the Insertion of Sulfur Dioxide and Its Preliminary Application Investigation 含二氧化硫的非活化n -烯烃-吲哚光诱导选择性环化级联反应及其初步应用研究

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-06 Epub Date: 2026-10-21 DOI: 10.1021/acs.joc.6c01943

Jiaqi Huang, Jiwei Li, Yuwei Zeng, Qichen Li, Yueyue Jia, Feng Liang, Zhenzhen Hu, You Mao, Jiangwei Tian, Min Yang

引用次数: 0

Room-Temperature Palladium-Catalyzed Aminative Suzuki–Miyaura Coupling of Arylthianthrenium Salts and Mechanistic Studies 室温钯催化芳硫钍盐胺基Suzuki-Miyaura偶联及其机理研究

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-06 Epub Date: 2026-10-24 DOI: 10.1021/acs.joc.6c02280

Bo-Sheng Zhang, Xin-Yue Fu, Feng Zhang, Long-Sheng Wang, Ke-Hu Wang, Xi-Cun Wang, Xue-Ya Gou, Yulai Hu, Yong-Min Liang

{"title":"Room-Temperature Palladium-Catalyzed Aminative Suzuki–Miyaura Coupling of Arylthianthrenium Salts and Mechanistic Studies","authors":"Bo-Sheng Zhang, Xin-Yue Fu, Feng Zhang, Long-Sheng Wang, Ke-Hu Wang, Xi-Cun Wang, Xue-Ya Gou, Yulai Hu, Yong-Min Liang","doi":"10.1021/acs.joc.6c02280","DOIUrl":"10.1021/acs.joc.6c02280","url":null,"abstract":"The development of novel catalytic transformations that repurpose classical reagents to directly access structurally diverse products from the same starting materials has garnered significant interest. By eliminating the need to separately synthesize and purify new reagents, the chemical space reachable from existing functionalized intermediates can be increased multifold. Nitrogen insertion strategies can convert the C–C bond formed in traditional Suzuki–Miyaura coupling into a C–N–C bond, substantially expanding the explorable chemical space. Herein, building upon the arylthianthrenium salt strategy, we have developed a room-temperature palladium-catalyzed nitrogen-atom insertion coupling reaction, providing a new retrosynthetic disconnection strategy that can be directly applied to the late-stage functionalization (LSF) of complex drug molecules. Notably, this intermolecular three-component aminative coupling proceeds smoothly at room temperature, which not only aligns with the principles of green chemistry by obviating the need for heating apparatus and light-irradiation equipment, but also reduces energy consumption while enhancing reaction safety. To probe the mechanism, control experiments were conducted, and the catalytic reaction was monitored by NMR spectroscopy. Based on these results and density functional theory (DFT) calculations, the barrier for the overall rate-determining step is only 16.5 kcal/mol, explaining the room-temperature reactivity.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 44","pages":"15139–15147"},"PeriodicalIF":3.3,"publicationDate":"2026-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241895","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

Mechanism and Origin of Regio- and Stereoselectivity in the Synthesis of Benzazocines via Palladium-Catalyzed [6+2] Annulation of Allenyl Benzoxazinanones with Terminal Allenes 钯催化[6+2]环化末端烯基苯并恶嗪酮合成苯并恶嗪的区域选择性和立体选择性机理及来源

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-06 Epub Date: 2026-10-21 DOI: 10.1021/acs.joc.6c01402

Jinglong Xin, Aili Feng, Jihong Xu, Yanling Zhao, Dongju Zhang

{"title":"Mechanism and Origin of Regio- and Stereoselectivity in the Synthesis of Benzazocines via Palladium-Catalyzed [6+2] Annulation of Allenyl Benzoxazinanones with Terminal Allenes","authors":"Jinglong Xin, Aili Feng, Jihong Xu, Yanling Zhao, Dongju Zhang","doi":"10.1021/acs.joc.6c01402","DOIUrl":"10.1021/acs.joc.6c01402","url":null,"abstract":"Density functional theory calculations were carried out to elucidate the mechanism and the origin of regio- and stereoselectivity in the palladium-catalyzed [6+2] annulation of allenyl benzoxazinanones with terminal allenes. An unconventional oxidative addition–reductive elimination mechanism was revealed. The reaction starts with SN2-type oxidative addition of the substrate to Pd0, followed by decarboxylation to afford a π-allylpalladium intermediate. Pathway bifurcation leads to competing [6+2] and [4+2] annulations, and the more stable seven-membered palladacycle kinetically favors the [6+2] pathway and inhibits the [4+2] side reaction. Distortion/interaction analysis indicates that the exclusive Z-selectivity originates from the larger structural distortion of the E-configured transition state. Different from conventional three-center reductive elimination, the reaction proceeds via a zwitterionic-intermediate-mediated nucleophilic coupling pathway, which acts as the rate-limiting step with an overall barrier of 21.3 kcal/mol. This work rationalizes experimental selectivity and offers theoretical guidance for the design of related Pd-catalyzed annulation reactions.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 44","pages":"14823–14832"},"PeriodicalIF":3.3,"publicationDate":"2026-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226579","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

Photoredox α-Alkylation of Phosphonates by Styrenes 苯乙烯光氧化还原膦酸盐α-烷基化反应

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-06 Epub Date: 2026-10-22 DOI: 10.1021/acs.joc.6c02170

Egor A. Drokin, Vladimir A. Abramov, Maxim A. Topchiy, Dilshodakhon K. Isaeva, Irina P. Beletskaya, Andrey F. Asachenko

引用次数: 0

Annulative Suzuki–Miyaura Coupling for the Synthesis of Highly Fluorescent Near-Infrared PAH[b]-Fused BODIPYs 环态Suzuki-Miyaura偶联合成高荧光近红外多环芳烃[b]-熔合BODIPYs

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-06 Epub Date: 2026-10-23 DOI: 10.1021/acs.joc.6c01809

Xiaowei Zhang, Yongli Zhang, Peixin Li, Ruihan Yang, Yanni Li, Yunfei Zhi, Tianding Hu, Shaoyun Shan, Yanhua Yang, Xiangguang Li

{"title":"Annulative Suzuki–Miyaura Coupling for the Synthesis of Highly Fluorescent Near-Infrared PAH[b]-Fused BODIPYs","authors":"Xiaowei Zhang, Yongli Zhang, Peixin Li, Ruihan Yang, Yanni Li, Yunfei Zhi, Tianding Hu, Shaoyun Shan, Yanhua Yang, Xiangguang Li","doi":"10.1021/acs.joc.6c01809","DOIUrl":"10.1021/acs.joc.6c01809","url":null,"abstract":"A one-pot annulative Suzuki–Miyaura strategy was developed for the synthesis of highly fluorescent, near-infrared (NIR)-emissive polycyclic aromatic hydrocarbon (PAH)-fused BODIPYs. Tetrahalogenated BODIPYs reacted with 1,2-bis(pinacolato)boryl arene or alkene via a fourfold cross-coupling/annulation cascade under Pd(PPh3)4 catalysis, furnishing phenanthro[b]- or naphtho[b]-fused products in 32–70% yields without isolation of intermediates. Single-crystal X-ray diffraction revealed slightly twisted frameworks (dihedral angles: 3.17–10.01°), and NICS(0) calculations confirmed strong local aromaticity. Photophysical studies displayed intense absorption at 658–675 nm and narrow NIR emission at 670–690 nm, together with small Stokes shifts (≤322 cm–1) and high fluorescence quantum yields (ΦF = 0.46–0.68). Their weak solvatochromism and substantial HOMO–LUMO overlap indicate that the emissive excited states are predominantly locally excited (LE) in character. Cyclic voltammetry demonstrated narrow electrochemical band gaps (1.51–1.70 eV) and low LUMO energy levels (–3.82 to –3.88 eV for 3a–c and 4e), while DFT and TD-DFT calculations showed that the lowest-energy excitation is dominated by a HOMO → LUMO π → π* transition. This modular annulation strategy provides concise access to rigid PAH-fused BODIPYs that combine efficient NIR emission with high fluorescence efficiency, offering a versatile platform for the development of advanced NIR fluorophores.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 44","pages":"14975–14986"},"PeriodicalIF":3.3,"publicationDate":"2026-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241899","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

Substrate-Controlled Copper-Catalyzed Regiodivergent Carboarylation-Ring Closure of Alkynyl Benzylphosphonates with Diaryliodonium Salts 底物控制的铜催化区域发散羰化-二芳基硫鎓盐对烷基苄基膦酸盐的封环作用

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-06 Epub Date: 2026-10-26 DOI: 10.1021/acs.joc.6c01751

Xingyu Tu, Bo Jiang, Danqing Wu, Xihao Niu, Zihao Jin, Zhiwei Miao

引用次数: 0

Defluorinative [3 + 3] Annulation Reaction of α-Fluoroacetamides with 2-Trifluoromethylalkenes for the Formation of Densely Functionalized Difluorinated δ-Lactams α-氟乙酰胺与2-三氟甲基烯的脱氟[3 + 3]环化反应生成密集功能化的二氟化δ-内酰胺

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-06 Epub Date: 2026-10-27 DOI: 10.1021/acs.joc.6c01845

Sanoop P. Chandrasekharan, Usha Yadav, Indrajith K. Biju, Shreeya Srivastava, Kishor Mohanan

引用次数: 0

A Unified Phosgene-Free Carbonylation Using CO2 for the Synthesis of Ureas, Carbamates, Carbonates, Amides, and Formamides 用CO2合成尿素、氨基甲酸酯、碳酸盐、酰胺和甲酰胺的统一无光气羰基化反应

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-06 Epub Date: 2026-10-27 DOI: 10.1021/acs.joc.6c01831

Lalit Malkania, Arun Kumar, Varun Kumar, Anil Rana, Pankaj Sharma, Nutan Sharma, Nidhi Sharma, Naveen Yadav, Dinesh Mahajan

{"title":"A Unified Phosgene-Free Carbonylation Using CO2 for the Synthesis of Ureas, Carbamates, Carbonates, Amides, and Formamides","authors":"Lalit Malkania, Arun Kumar, Varun Kumar, Anil Rana, Pankaj Sharma, Nutan Sharma, Nidhi Sharma, Naveen Yadav, Dinesh Mahajan","doi":"10.1021/acs.joc.6c01831","DOIUrl":"10.1021/acs.joc.6c01831","url":null,"abstract":"Phosgene remains a privileged reagent for carbonylation; however, its extreme toxicity and stringent regulatory controls often restrict its routine and broad application. Herein, we describe a unified CO2-based carbonylation platform for the synthesis of ureas, (thio)carbamates, (thio)carbonates, amides, and formamides under mild, metal-free conditions. The method employs readily available phosphorus(V) activators to generate transient phosphorus-activated carbonyl species that selectively react with amines, alcohols, thiols, hydrides, and organometallic reagents, enabling a one-pot, three-component protocol that telescopes multi-step phosgene-based sequences into a single operation. This approach eliminates the need for phosgene and other preactivated carbonylating reagents. Mechanistic studies are most consistent with the involvement of a transient phosphorus-mediated carbonylating species, conceptually analogous to electrophilic carbonyl transfer in biological systems, although its precise identity remains unresolved. The synthetic utility of the platform is demonstrated by the 25 g synthesis of the anticancer drug sorafenib using POCl3 as the activator. By harnessing CO2 as a C1 synthon, this strategy addresses a long-standing challenge in electrophilic carbonylation and provides an operationally simple and complementary alternative to phosgene-based methods.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 44","pages":"14993–15002"},"PeriodicalIF":3.3,"publicationDate":"2026-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149251014","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

Synthesis of 2-Amidothiophenes via Fiesselmann-Type Annulation of Activated Ynamides 活化酰胺fiesselmann型环法制备2-氨基噻吩

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-06 Epub Date: 2026-10-28 DOI: 10.1021/acs.joc.6c01134

Marco Menghini, Laurence Miesch

引用次数: 0