Journal of Organic Chemistry最新文献_第7页

Multi-Ion Complexes and Competition from Bulky BArF- Anions for Chloride Binding in Ion Pairing Conditions. 离子对条件下多离子配合物和大块BArF-阴离子对氯离子结合的竞争。

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2025-10-09 DOI: 10.1021/acs.joc.5c01750

Amanda R Morgan,Janine M Holleworth,Nabarupa Bhattacharjee,Amar H Flood

{"title":"Multi-Ion Complexes and Competition from Bulky BArF- Anions for Chloride Binding in Ion Pairing Conditions.","authors":"Amanda R Morgan,Janine M Holleworth,Nabarupa Bhattacharjee,Amar H Flood","doi":"10.1021/acs.joc.5c01750","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01750","url":null,"abstract":"Cationic charges have long been used to enhance anion binding. Embedding charge introduces strong ion pairing for target anions but also for off-target ions, ultimately generating a mixture of multi-ion species that are hard to identify and quantify. While many sidestep this problem using polar solvents and weakly coordinating ions, these approaches exclude a substantial cross-section of conditions found in applications spanning recognition, assembly, separations, templation, and catalysis. To confront this complexity, we study the binding of an anion to a cationic receptor featuring low shape complementarity in a low-polarity solvent to maximize ionic interactions. We prepared the receptor as a salt of the weakly coordinating tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF-) anion and studied the binding of small chloride (Cl-) and medium-sized iodide (I-) anions. Surprisingly, the use of the bulky BArF- anion does not suppress ion pairing interactions, with 65% of the receptor being paired at 0.5 mM in dichloromethane. We observe multi-ion receptor-Cl- complexes (2:1, 1:1, 1:2), reinforcing the complexity that emerges when working in low-polarity media. We reveal the dependence of affinity on anion charge density and size and that bulky BArF- counteranions compete for chloride binding. These studies reveal the noninnocence of BArF- anions and strategies to quantify multi-ion species.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"45 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145254675","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

A Family of Helical BN-Nanographenes: Systematic Synthesis, Structures, and Properties of Heterole-Fused Carbazole Azaborine Dimers 一类螺旋bn -纳米石墨烯：杂合咔唑氮杂硼二聚体的系统合成、结构和性能。

IF 3.6 2区化学

Journal of Organic Chemistry Pub Date : 2025-10-09 DOI: 10.1021/acs.joc.5c01330

Koji Yamamoto*, , , Nanako Kiuchi, , , Karen Hara, , , Koji Yamamoto, , and , Yosuke Nakamura,

{"title":"A Family of Helical BN-Nanographenes: Systematic Synthesis, Structures, and Properties of Heterole-Fused Carbazole Azaborine Dimers","authors":"Koji Yamamoto*, , , Nanako Kiuchi, , , Karen Hara, , , Koji Yamamoto, , and , Yosuke Nakamura, ","doi":"10.1021/acs.joc.5c01330","DOIUrl":"10.1021/acs.joc.5c01330","url":null,"abstract":"Replacing two carbon atoms with neighboring boron–nitrogen (B–N) units in helical polycyclic aromatic hydrocarbons can substantially improve the photophysical properties, whereas the reports have remained scarce with underdeveloped structure–property relationships. We herein report the synthesis and physicochemical properties of a series of heterole-fused dimers of carbazole-containing azaborines as a new family of helical BN-nanographenes. We synthesized the carbazole azaborine dimers fused with N-butylpyrrole (1a), N-phenylpyrrole (1b), furan (2), thiophene (3a), selenophene (4), and thiophene S-dioxide (5) via double electrophilic borylation of rationally designed precursors as a key step. Thiophene-fused 3b and 3c bearing smaller terminal substituents than 3a were also synthesized. The central heterole had distinct effects on the electrochemical and photophysical properties, accompanied by strong emission of 1a, 1b, and 2 with fluorescence quantum yields of 0.51–0.56. The bulkiness of the terminal substituents had negligible effects on the properties in solution but markedly affected the crystal packing mode and fluorescence properties in the solid state. The structural effects on the electronic structures were also discussed with the aid of theoretical calculations.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14487–14499"},"PeriodicalIF":3.6,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246467","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

Diastereoselective Synthesis of 3-(Aminoalkylidene)oxindoles via a Nucleophilic Vinylic Substitution of 2-Chloropyridinium Salts 2-氯吡啶盐亲核乙烯取代非对映选择性合成3-（氨基烷基基）氧吲哚。

IF 3.6 2区化学

Journal of Organic Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.joc.5c00728

Hamideh Shirazi, , , Kaveh Imani, , , Behrouz Notash, , and , Ayoob Bazgir*,

引用次数: 0

Visible-Light-Driven One-Pot Synthesis of Polycyclic-Fused Amino-Thiazoles and Amino-Selenazoles via HFIP-Promoted Multicomponent Cyclizations hfip促进多组分环化，可见光驱动一锅法合成多环熔合氨基噻唑和氨基硒唑。

IF 3.6 2区化学

Journal of Organic Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.joc.5c01525

Nurabul Mondal, , , Sunidhi Raj, , and , Lokman H. Choudhury*,

引用次数: 0

Microwave-Driven Solventless Nickel Metalloradical-Catalyzed [2 + 2 + 1 + 1] Cascade Annulation of Polysubstituted Pyridines 微波驱动无溶剂镍金属催化[2 + 2 + 1 + 1]级联环化多取代吡啶

IF 3.6 2区化学

Journal of Organic Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.joc.5c01531

Debashis Jana, , , Sampad Malik, , , Gopal Kanrar, , and , Kausikisankar Pramanik*,

{"title":"Microwave-Driven Solventless Nickel Metalloradical-Catalyzed [2 + 2 + 1 + 1] Cascade Annulation of Polysubstituted Pyridines","authors":"Debashis Jana, , , Sampad Malik, , , Gopal Kanrar, , and , Kausikisankar Pramanik*, ","doi":"10.1021/acs.joc.5c01531","DOIUrl":"10.1021/acs.joc.5c01531","url":null,"abstract":"We demonstrate an eco-friendly and efficient method for the synthesis of biologically relevant polysubstituted pyridines, including pentasubstituted derivatives, using a homogeneous nickel–metalloradical catalyst. This solvent-free strategy under microwave (MW) irradiation employs readily available primary and secondary aryl alcohols along with ammonium acetate to form pyridine scaffolds via catalytic dehydrogenative alcohol oxidation, yielding 68–93% under neat conditions. The MW-assisted four-component (4CRs) domino [2 + 2 + 1 + 1] annulation proceeds through consecutive C–C and C–N bond formations, followed by catalytic dehydrogenative aromatization. The nickel–metalloradical drives dual catalytic cycles: alcohol dehydrogenation and ring aromatization, both via single-electron-transfer (SET) pathways. This one-pot methodology requires only 20 mol % base loading, achieving excellent turnover number (TON ≈ 104) with short residence time (2 h). A wide variety of primary and secondary alcohols have been successfully utilized as substrates (61 examples). Notably, this open-air sustainable approach generates only benign byproducts (H2O, H2O2) without external oxidants or additives. This convenient and cost-effective strategy aligns with green chemistry principles, ensuring simplicity and excellent E-factor values (0.3–0.5), marking a significant advance in highly functionalized pyridine synthesis.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14579–14596"},"PeriodicalIF":3.6,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241817","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

Water-Promoted Indole Migration of Bis(indol-3-yl)-ynamides Using Zn(OTf)2 as a Lewis Acid Catalyst Zn(OTf)2作为Lewis酸催化剂，水促进双（吲哚-3-基）-酰胺的吲哚迁移

IF 3.6 2区化学

Journal of Organic Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.joc.5c01620

Zhanshuai Xiao, , , Yin Wei*, , and , Min Shi*,

引用次数: 0

From Monomers to Nanocapsules: The Role of Structural Features in Amino-Acid-Derived BTA Self-Assembly 从单体到纳米胶囊：结构特征在氨基酸衍生的BTA自组装中的作用。

IF 3.6 2区化学

Journal of Organic Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.joc.5c01500

Anna Walczak, , , Grzegorz Markiewicz, , , Michał Gliński, , , Miroslava Čonková, , and , Artur R. Stefankiewicz*,

引用次数: 0

Origin of Substituent-Modulated Regioselectivity in Phosphine-Catalyzed [3 + 2] Cyclization of Allenoates and Enones: A Kinetic Shift toward Curtin–Hammett Control 膦催化的[3 + 2]烯丙酸酯和烯酮环化中取代基调制区域选择性的起源：向Curtin-Hammett控制的动力学转变

IF 3.6 2区化学

Journal of Organic Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.joc.5c01466

Gou-Tao Huang*, and , Jen-Shiang K. Yu*,

{"title":"Origin of Substituent-Modulated Regioselectivity in Phosphine-Catalyzed [3 + 2] Cyclization of Allenoates and Enones: A Kinetic Shift toward Curtin–Hammett Control","authors":"Gou-Tao Huang*,  and , Jen-Shiang K. Yu*, ","doi":"10.1021/acs.joc.5c01466","DOIUrl":"10.1021/acs.joc.5c01466","url":null,"abstract":"The phosphine-catalyzed [3 + 2] cycloaddition of allenoates with enones provides an efficient route to five-membered carbocycles and exhibits regioselectivity that depends on the substituents of the substrates. To elucidate the origin of the substituent effects, density functional theory calculations and kinetic modeling are performed on the reactions of unsubstituted/substituted allenoates (2/8) with arylideneoxindoles (e-iii). Nucleophilic attack of PPh3 on the allenoate generates interconvertible Z-, E-, and twisted adducts: the former two participate in regioselective [3 + 2] cyclization. For 2, the major γ-regioisomeric product forms via the E-adduct. Kinetic modeling predicts an α:γ ratio of 1:99, consistent with the experimentally observed 10:90 selectivity. By contrast, the reaction of 8 yields the α-regioisomer via the Z-adduct. The computed isomer ratio of 99:1 agrees with the experimental value of >95:5. The switch in regioselectivity is attributed to the interplay between electronic and steric effects. Secondary orbital interactions favor the γ-[3 + 2] pathway. Substituent-induced steric hindrance is found to elevate the activation barriers to cyclization, thereby shifting the kinetic regime toward Curtin–Hammett control and modulating regioselectivity. These findings highlight the pivotal role of adduct dynamics in phosphine catalysis and clarify the conditions under which Curtin–Hammett control governs product selectivity.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14541–14556"},"PeriodicalIF":3.6,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.joc.5c01466","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241818","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}

引用次数: 0

Electrochemical Acceptorless Dehydrogenation of N-Heterocycles: Sustainable Synthesis of Aromatic Compounds with Hydrogen Release n -杂环的电化学无受体脱氢：释放氢可持续合成芳香族化合物

IF 3.6 2区化学

Journal of Organic Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.joc.5c01101

Shiwen Fu, , , Weihang Li, , , Hangxuan Wu, , , Gongyuan Zhao, , , Zhonghui Sun*, , , Jinsong Peng*, , and , Chunxia Chen*,

引用次数: 0

Visible-Light-Sponsored Organophotoredox-Catalyzed Synthesis of Diverse Sulfones from Unsaturated Entities Using DABSO as a SO2 Source 以DABSO为SO2源，可见光赞助的有机光氧化还原催化不饱和实体合成多种砜

IF 3.6 2区化学

Journal of Organic Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.joc.5c01881

Md Tanjul Hoque, , , Pintu Pratihar, , , Prakash K. Mandal, , , Aranya Das, , , Rajjakfur Rahaman*, , and , Dilip K. Maiti*,

引用次数: 0