Journal of Organic Chemistry最新文献

Intermolecular Dearomative Alkylation–Cyclization Cascade of β-Aryltryptophols: Diastereoselective Access to Furoindolines with Three Contiguous Stereocenters

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-12 DOI: 10.1021/acs.joc.6c02187

Upasana Deka,Sajal Kumar Das

{"title":"Intermolecular Dearomative Alkylation–Cyclization Cascade of β-Aryltryptophols: Diastereoselective Access to Furoindolines with Three Contiguous Stereocenters","authors":"Upasana Deka,Sajal Kumar Das","doi":"10.1021/acs.joc.6c02187","DOIUrl":"https://doi.org/10.1021/acs.joc.6c02187","url":null,"abstract":"Intermolecular dearomative C3-alkylation of indoles bearing an adjacent, sterically encumbered stereocenter presents a dual challenge: overcoming substantial steric hindrance to achieve efficient reactivity and attaining high facial diastereoselectivity. Herein, we report a NaOtBu/Et3B-promoted intermolecular dearomative alkylation–cyclization cascade of β-aryltryptophols that addresses both challenges, affording furoindolines bearing three contiguous stereogenic centers in yields of up to 88%, with the endo-diastereomers consistently obtained as the major products (up to 11.2:1 endo/exo d.r.). The method was demonstrated across 36 examples, incorporating allylic, benzylic, and propargyl bromides as well as methyl iodide, and accommodating diverse electronic variations on both the indole nucleus and the pendant aryl ring of the β-aryltryptophol substrates. An enantioenriched substrate underwent the reaction without detectable racemization (>99:1 e.r.), indicating retention of the pre-existing stereocenter and its stereochemical relay to the newly formed stereocenters. An α-aryltryptophol, in which the stereogenic center is one atom farther from the indole C3 position, also underwent the cascade process, although the corresponding exo-diastereomers were isolated as the major products (up to 5.2:1 exo/endo d.r.).","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"9 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374803","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

Radical Anion-Driven, Photocatalyst-Free α-Aminoalkylation of Quinoxalin-2(1H)-ones

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-10 DOI: 10.1021/acs.joc.6c02100

Nawaphon Saartaiam,Naiyana Saesian,Tomohiro Isono,Rungroj Saruengkhanphasit,Somsak Ruchirawat,Worawat Niwetmarin

引用次数: 0

Rapid and Green One-Pot Synthesis in Water: Accessing Polypeptides with Two Disulfide Bridges

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-10 DOI: 10.1021/acs.joc.6c00846

Bin Zhang,Cunlin Wang,Zirui Lü,Yongbiao Guo,Zhenhua Gao,Yulong Li,Xiandong Dai,Fanhua Meng

{"title":"Rapid and Green One-Pot Synthesis in Water: Accessing Polypeptides with Two Disulfide Bridges","authors":"Bin Zhang,Cunlin Wang,Zirui Lü,Yongbiao Guo,Zhenhua Gao,Yulong Li,Xiandong Dai,Fanhua Meng","doi":"10.1021/acs.joc.6c00846","DOIUrl":"https://doi.org/10.1021/acs.joc.6c00846","url":null,"abstract":"Regioselective assembly of multiple disulfide bonds in peptides remains a formidable challenge in synthetic peptide chemistry. In this work, a rapid, eco-friendly one-pot strategy for the regioselective synthesis of polypeptides bearing two disulfide bonds was developed. The first disulfide bond was formed via hydrogen peroxide-mediated oxidation of dithiol precursors in water, and the second was subsequently established through iodine-triggered deprotection of two acetamidomethyl (Acm) groups under acidic conditions. Using this protocol, a series of bioactive bicyclic peptides with diverse disulfide topologies were efficiently synthesized, with overall isolated yields ranging from 54% to 74%. Remarkably, this method exhibits excellent tolerance toward Trp- and Tyr-containing peptides with no detectable oxidative byproducts; nevertheless, it cannot be applied to Met-bearing peptides, as the thioether side chain of methionine undergoes preferential oxidation. In contrast to previously reported one-pot synthetic methodologies, this approach eliminates buffers and metallic reagents, simplifies the reaction workflow, and employs pure water as the exclusive solvent alongside inexpensive, commercially available reagents. Accordingly, it serves as a mild, efficient, and environmentally benign alternative for the synthesis of two-disulfide-bridged peptides.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374802","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

Electro- and Mechanochemical N-Cyanomethylation and N-Selenylation of a Diverse Array of Biorelevant Aryl(Heteroaryl) Hydrazones: A Robust Dual Green Synthetic Approach

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-10 DOI: 10.1021/acs.joc.6c02013

Pintu Karmakar,Koushik Pal,Goutam Brahmachari

{"title":"Electro- and Mechanochemical N-Cyanomethylation and N-Selenylation of a Diverse Array of Biorelevant Aryl(Heteroaryl) Hydrazones: A Robust Dual Green Synthetic Approach","authors":"Pintu Karmakar,Koushik Pal,Goutam Brahmachari","doi":"10.1021/acs.joc.6c02013","DOIUrl":"https://doi.org/10.1021/acs.joc.6c02013","url":null,"abstract":"We herein disclose a dual synthetic approach involving electrochemical and mechanochemical strategies for the N-cyanomethylation and N-selenylation of aryl(heteroaryl) hydrazones, thereby accessing a new series of diversely functionalized aryl(heteroaryl) hydrazinyl acetonitriles and aryl(heteroaryl) hydrazinyl phenylselenides, respectively. Both methods are fruitfully applicable to the N-cyanomethylation of a group of N-heterocycles. This dual approach highlights the synergy between electrochemistry and mechanochemistry as green and sustainable platforms for constructing value-added nitrile- and organoselenium molecules relevant to medicinal and materials chemistry. The key advantages of these newly developed, green chemistry-driven methodologies include mild reaction conditions using green energy tools, the avoidance of transition metal catalysts, external oxidants, hazardous cyanide sources, and reacting solvents (mechanochemical), a broad substrate scope with excellent functional-group tolerance, good to excellent yields, short reaction times (in minutes), the reusability of the solid surface (mechanochemical), operational simplicity, low E-factors (mechanochemistry), higher Faradaic efficiency (electrochemical), and eco-friendliness. Gram-scale synthesis and late-stage synthetic application of the hydrazinyl acetonitrile compound have also been demonstrated.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"20 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374804","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

Pd-Catalyzed Dearomative [4 + 2] Annulation of 3-Substituted NH-Indoles with 2-Methylenepropane-1,3-diol and Its Mono-Aza Variant

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-10 DOI: 10.1021/acs.joc.6c02137

Kriti Yadav,Sajal Kumar Das

引用次数: 0

Electrochemically Driven Denitrogenative Thiolation of 1,2,3-Benzotriazin-4(3H)-ones with Thiols

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-10 DOI: 10.1021/acs.joc.6c01743

Sanfei Nian,Jiawei Zhang,Yue Yu,Jingting Yu,Ke Wei,Xujiao Yang,Shengming Lu,Min Liu,Qiuyue Song

引用次数: 0

Direct C3-Cyanation of Indoles Enabled by Cyanobenziodoxolone (CBX) and HFIP 三苯并碘唑酮（CBX）与HFIP催化吲哚直接c3 -氰化反应

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-09 DOI: 10.1021/acs.joc.6c00750

Cong Li,Zhijian Wang,Xiangyu Zhan,Dan Xiao,Yingjie Gao,Yunfei Du

引用次数: 0

Acidic C─H Functionalization to Access Ketoalkyl-Substituted Quinazolinones by Visible-Light Photoredox Catalysis. 可见光光氧化还原催化酸性C─H功能化制备酮烷基取代喹唑啉酮。

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-09 DOI: 10.1021/acs.joc.6c01915

Hao Lin, Wan-Lei Yu, Zhiming Wang, Jianguo Yang

引用次数: 0

Solvent-Controlled Switching between Electron Transfer and Type II Photosensitization in a Zinc Phthalocyanine–Flavonol Pair 酞菁锌-黄酮醇对中电子转移和II型光敏化的溶剂控制切换

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-09 DOI: 10.1021/acs.joc.6c02231

Filip Svěrák,Jana Okoročenkova,Josef Filgas,Petr Slavíček,Petr Klán

{"title":"Solvent-Controlled Switching between Electron Transfer and Type II Photosensitization in a Zinc Phthalocyanine–Flavonol Pair","authors":"Filip Svěrák,Jana Okoročenkova,Josef Filgas,Petr Slavíček,Petr Klán","doi":"10.1021/acs.joc.6c02231","DOIUrl":"https://doi.org/10.1021/acs.joc.6c02231","url":null,"abstract":"The impact of solvent nature on intermolecular interactions within a pair of phthalocyanine and 3-hydroxyflavone (flavonol) derivatives was examined with the aim of activating the UV-absorbing flavonol chromophore by visible/NIR light. Unlike its metal-free analog, Zn-phthalocyanine was found to form a 1:1 complex with flavonol in nonpolar dichloromethane. This complex showed near-diffusion-limited quenching of phthalocyanine fluorescence, which, however, did not lead to flavonol emission or triplet reactivity. A thorough examination of high-level DLPNO-CCSD(T)/CBS and constrained DFT electronic structure calculations revealed that photoinduced electron transfer within the excited complex is thermodynamically feasible. Concurrently, the formation of carbon monoxide from flavonol was observed, facilitated by singlet oxygen, generated by a Type II sensitization via triplet-excited phthalocyanine. In dimethyl sulfoxide (DMSO), solvent ligation inhibited phthalocyanine/flavonol complexation, and a Type II photosensitization was almost exclusively responsible for the flavonol oxygenation. The suppression of this reaction pathway in degassed DMSO resulted in intermolecular quenching of the phthalocyanine triplet by the flavonol moiety. The Wigner sampling of the T1–S0 energy gaps indicates that intramolecular proton transfer can decrease the flavonol triplet energy sufficiently to enable a nonvertical proton-coupled energy-transfer pathway from phthalocyanine to flavonol. Although this pathway is energetically accessible, it is inefficient.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"75 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360243","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

Lactonization-Controlled Electrostatic Potential Redistribution for Modulating Intramolecular Charge Transfer and Luminescent Behavior 内酰胺化控制的静电电位重分配用于调节分子内电荷转移和发光行为

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2026-11-09 DOI: 10.1021/acs.joc.6c01730

Fei Meng,Xue-Ying Zhang,Rui Han,Ya-Yu Wang,Xin-Ge Wu,Ling Liang,Ming-Xia Zhang,Wen-Xuan Zhao,Hong-Tao Lin,Shu-Hai Chen,Chuan-Zeng Wang

{"title":"Lactonization-Controlled Electrostatic Potential Redistribution for Modulating Intramolecular Charge Transfer and Luminescent Behavior","authors":"Fei Meng,Xue-Ying Zhang,Rui Han,Ya-Yu Wang,Xin-Ge Wu,Ling Liang,Ming-Xia Zhang,Wen-Xuan Zhao,Hong-Tao Lin,Shu-Hai Chen,Chuan-Zeng Wang","doi":"10.1021/acs.joc.6c01730","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01730","url":null,"abstract":"Four cyanoethylene-functionalized pyrene derivatives were synthesized via Suzuki coupling and subsequent hydrolysis-triggered lactonization. Substituent effects exert pronounced and consistent modulation of photophysical properties both in dilute solution and in the aggregated state. TriFPy exhibited the most significant redshift centered at 508 nm in solution and the highest photoluminescence quantum yield (ΦFL = 60%). BuTriFPy, possessing the smallest calculated HOMO–LUMO energy gap (ΔEg = 3.14 eV), displayed dual emission in dilute solution and the longest solid-state fluorescence lifetime (τ = 3.34 ns). The excellent mechanofluorochromism (MFC) performance and reversible switching behavior of the four materials were rationalized and experimentally corroborated by their microcrystalline architectures and corresponding X-ray diffraction (XRD) patterns. Notably, polymer-induced emission enhancement (2–5 times) and blueshifted emission represent promising design strategies that broaden the applicability of these materials in optoelectronic and flexible material applications. Moreover, the PhPy-based fluorescent extractant can realize high-contrast and high-sensitivity visual extraction of latent fingerprints (LFPs).","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368389","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