{"title":"Rhodium-Catalyzed C–H Heteroarylation and Alkenylation of N-Phenoxyacetamides Using Iodonium Ylides","authors":"Wenqian Ding, , , Wanqi Hu, , , Weiqi Liu, , and , Xiaowei Wu*, ","doi":"10.1021/acs.joc.5c00858","DOIUrl":"10.1021/acs.joc.5c00858","url":null,"abstract":"<p >Herein, we describe a rhodium-catalyzed monoheteroarylation and alkenylation of <i>N-</i>phenoxyacetamides using iodonium ylides derived from cyclo-1,3-diones. This approach efficiently delivers novel heteroarylated and alkenylated products under mild reaction conditions. The protocol showcases good functional group tolerance and a wide substrate scope. Furthermore, this allows for smooth scale-up synthesis. Additional transformation experiments were conducted to highlight the potential synthetic utility of this methodology.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14373–14382"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229201","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}
{"title":"Base-Promoted Nucleophile Addition to Arynes Generated from Triaryloxonium Salts","authors":"Sheng Fang, , , Wang-Liang Chen, , , Yuan-Jie Meng, , , Lian-Bao Ye*, , , Shang-Shi Zhang*, , and , Bing Shu*, ","doi":"10.1021/acs.joc.5c01258","DOIUrl":"10.1021/acs.joc.5c01258","url":null,"abstract":"<p >In this study, a facile method for the synthesis of aryl-substituted esters, amides, α-aryl sulfoxonium ylides, thioethers, aryl-quinolinones/isoquinolinones via nucleophilic addition reaction of oxonium aryne precursors with corresponding carboxylic acids, isocyanides, sulfoxonium ylides, mercaptans, trifluoromethyl silver, and halogenated quinolines/isoquinolines has been developed. This protocol featured mild reaction conditions, a high yield, and a good tolerance of functional groups. In addition, scale-up synthesis and related applications were also accomplished.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14452–14463"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235933","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}
{"title":"N-Doped π-Extended Coumarins: Synthesis and Photophysical Properties of Isoquinoline and Pyrimidine-Fused Coumarins","authors":"Rajashree Bhuyan, and , Pranjal Gogoi*, ","doi":"10.1021/acs.joc.5c01379","DOIUrl":"10.1021/acs.joc.5c01379","url":null,"abstract":"<p >We present here a novel series of <i>N</i>-doped π-extended coumarins derived from 4-aminocoumarin. Lewis and Bronsted acids mediated synthetic processes have been adopted for their synthesis, enabling the formation of C–C and C–N bonds under transition-metal-free conditions. This previously unexplored process delivers the target π-extended coumarins in good yields and provides access to isoquinoline- and pyrimidine-fused ring systems. Photophysical properties of the resulting compounds were investigated using UV–vis absorption and fluorescence emission spectroscopy. The synthesized compounds exhibit good fluorescence properties, highlighting their potential application for optoelectronic devices and as probes for bioimaging.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14500–14514"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235931","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}
Harnimarta Deol, , , Matthew H. Dixon, , , Hazel A. Fargher, , , Jacob Mayhugh, , , Bipin Pandey, , , Hyun Meen Park, , , Ava Raeisbahrami, , and , Eric V. Anslyn*,
{"title":"The Use of 5-Exo- and 6-Exo-Trig Cyclizations in the Manipulation and Degradation of Biotic and Abiotic Polymers","authors":"Harnimarta Deol, , , Matthew H. Dixon, , , Hazel A. Fargher, , , Jacob Mayhugh, , , Bipin Pandey, , , Hyun Meen Park, , , Ava Raeisbahrami, , and , Eric V. Anslyn*, ","doi":"10.1021/acs.joc.5c01633","DOIUrl":"10.1021/acs.joc.5c01633","url":null,"abstract":"<p >This JOCSynopsis underscores the pivotal role of 5-exo-trig and 6-exo-trig cyclization pathways in directing ring-closure reactions, with a focus on their application to the modification of biotic polymers, including amino acid labeling and N-terminal capping strategies in peptide stapling. This work extends these cyclizations to the degradation of both abiotic and biotic polymers. It also explores instances where degradation occurs through less favorable cyclization pathways, highlighting the complexity and context-dependence of these transformations. Additionally, it showcases the use of 5-exo-trig cyclization in reversible click chemistry, emphasizing its role in the design of dynamic materials. These insights are exemplified by systems such as a Meldrum’s acid-derived conjugate acceptor, which can undergo reversible “click” and “declick” processes, paving the way for the development of polymers with tunable and responsive properties.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14349–14362"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229198","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}
{"title":"Electrochemical Trifluoromethylation/Cyclization of N′-Arylidene-N-acryloyltosylhydrazides for the Synthesis of CF3-Substituted Pyrazolones","authors":"Yu Xia*, , , Wenlong Xu, , , Xinquan Wu, , , Tingting Yin, , , Shaofeng Wu, , , Ziren Chen, , , Bin Wang, , , Yonghong Zhang, , and , Chenjiang Liu*, ","doi":"10.1021/acs.joc.5c01197","DOIUrl":"10.1021/acs.joc.5c01197","url":null,"abstract":"<p >Herein, a mild and efficient synthesis of pyrazolones is disclosed through a sustainable electrochemical method. This electrolysis relied on cascade trifluoromethylation/cyclization by using CF<sub>3</sub>SO<sub>2</sub>Na as a trifluoromethyl source, which occurred directly at the anode. Two C–C bonds were formed to afford a series of novel trifluoromethyl-containing pyrazolone scaffolds without the addition of metals and redox reagents. Further mechanistic results showed that the reaction process may undergo a radical pathway.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14429–14438"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235934","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}
{"title":"Divergent Transformation of Diarylethanones via Anodic Oxidation and Electrochemical Baeyer–Villiger Oxidation for Scalable Synthesis of α-Acyloxyketones","authors":"Weihui Zhuang, , , Yumei Chen, , , Xin Ruan, , , Xiaofeng Zhang, , and , Qiufeng Huang*, ","doi":"10.1021/acs.joc.5c01580","DOIUrl":"10.1021/acs.joc.5c01580","url":null,"abstract":"<p >A divergent electrochemical transformation of diarylethanones using molecular oxygen and electricity as green oxidants provides a sustainable and scalable strategy for synthesizing α-acyloxyketone compounds. Mechanistic studies reveal bromide-mediated generation of a benzyl radical cation intermediate, which undergoes divergent reaction pathways: (i) anodic oxidation to a benzyl cation or (ii) reaction with cathodically generated O<sub>2</sub><sup>•–</sup> followed by Baeyer–Villiger oxidation to a carboxylate anion.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14607–14619"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229197","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}
{"title":"Direct Access to 1,3-Enynes from Skipped Enynes via HFIP-Promoted Allylic Substitution Reaction","authors":"Srinivasarao Yaragorla*, , , Aayesha Shaik, , and , Vinod Megavath, ","doi":"10.1021/acs.joc.5c01618","DOIUrl":"10.1021/acs.joc.5c01618","url":null,"abstract":"<p >A simple, efficient, and metal-free protocol for the synthesis of highly functionalized 1,3-enynes has been developed from skipped enynes by a direct nucleophilic substitution reaction in HFIP at room temperature in open air. This metal-free approach offers a broad substrate scope with excellent yields, Z-selective enynes, and atom economy.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14620–14626"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235935","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}
{"title":"o-Diiodobenzene/NaH Benzyne System Enables the Synthesis of Alkyl Aryl Ethers and Diaryl Ethers","authors":"Cong Xiao, , , Dianfan Liu, , , Xinhao Li, , , Wenjing Zhu, , , Qihui Wang, , , Tingting Yi, , , Xuejun Liu, , , Xiaodong Chen, , , Shilei Zhang*, , and , Yanwei Hu*, ","doi":"10.1021/acs.joc.5c01905","DOIUrl":"10.1021/acs.joc.5c01905","url":null,"abstract":"<p >We present here the application of <i>o</i>-diiodobenzene/NaH as an efficient benzyne system in reactions with various alcohols and phenols for the synthesis of alkyl aryl ethers and diaryl ethers. Compared to existing protocols for constructing aryl ethers, our new approach not only employs inexpensive and readily available starting materials with simple operation but also enables the preparation of sterically hindered <i>tert</i>-butyl aryl ethers and polyhalogenated diaryl ethers, which pose significant challenges to conventional methods. Additionally, the products retain an <i>ortho</i>-iodine substituent, facilitating further functionalization to access more complex molecular architectures.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14827–14834"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229195","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}
{"title":"Palladium-Catalyzed Benzylation/Semipinacol Rearrangement for the Construction of 3-Quaternary Carbon 2-Spiroindoline","authors":"Xin Chang, , , Kun-Shan Xue, , , Hai-Yan Tao*, , and , Chun-Jiang Wang, ","doi":"10.1021/acs.joc.5c02013","DOIUrl":"10.1021/acs.joc.5c02013","url":null,"abstract":"<p >The 3-quaternary carbon 2-spiroindoline scaffold occupies a significant position in both medicinal and synthetic chemistry. While the dearomatization of indoles represents the most direct and efficient route to such structural units, considerable limitations persist. Herein, utilizing 2-cyclobutanol-3-substituted indoles and benzyl phosphates as model substrates, we developed a novel Pd/BEt<sub>3</sub> synergistic catalyzed tandem benzylation/semipinacol rearrangement. This strategy efficiently constructs a series of 3-quaternary carbon 2-spiroindolines in high yields with excellent chemoselectivity and diastereoselectivity. Furthermore, this catalytic cascade reaction proceeds efficiently in a one-pot manner, as the thermally driven semipinacol rearrangement circumvents the need for intermediate isolation.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14796–14804"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235932","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}
{"title":"Mechanism of 3-O-Acyl-Directed α-Mannopyranosylation and Rationalization of the Contrasting Behavior of 3-O-Acyl Glucopyranosyl Donors","authors":"Shuay Abdullayev, and , David Crich*, ","doi":"10.1021/acs.joc.5c01978","DOIUrl":"10.1021/acs.joc.5c01978","url":null,"abstract":"<p >An investigation into the α-directing effect of 3-<i>O</i>-acyl groups in 4,6-<i>O</i>-benzylidene-directed mannopyranosylation is reported. No evidence was found by VT NMR experiments with <sup>13</sup>C-enriched 3-<i>O</i>-benzoyl esters for the formation of a bridged ion. Inclusion of an axial 3-<i>C</i>-methyl group in the donors to destabilize the ester ground-state conformation and promote participation enabled the observation of a very minor bridged ion in the NMR experiments. In experiments conducted in the presence of diphenyl sulfoxide, the only species observed were the two mannosyl oxysulfonium ions, yet the reactions were still extremely α-selective. Overall, no support was found for participation by the ester at the 3-position as the main pathway for α-selectivity. An alternative hypothesis is advanced based on acceptor hydrogen bonding to the acyl group, which is oriented in its ground state toward the anomeric position and so is ideally placed to participate in such hydrogen bonding. The much weaker α-directing effect of a 3-<i>O</i>-acyl group in the glucopyranosyl series is explained by the steric clash with the equatorial substituent at C2, which interferes with the stereodirecting hydrogen bond, and by the ground-state conformation of the 3-<i>O</i>-acyl group that is less well-disposed for the acceptor–donor hydrogen bond.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14769–14785"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.joc.5c01978","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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