Asian Journal of Organic Chemistry最新文献_第3页

Four‐Center Two‐Electron Bond in 3,6‐Di(tert‐butyl)naphthalene‐1,8‐diyl Bis(tert‐butyl Nitroxide) 3,6 -二（叔丁基）萘- 1,8 -二基二（叔丁基）硝基中的四中心二电子键

IF 2.8 4区化学

Asian Journal of Organic Chemistry Pub Date : 2025-05-01 DOI: 10.1002/ajoc.202500049

Rina Takano , Rika Uesugi , Daichi Iida , Prof. Dr. Takayuki Ishida

{"title":"Four‐Center Two‐Electron Bond in 3,6‐Di(tert‐butyl)naphthalene‐1,8‐diyl Bis(tert‐butyl Nitroxide)","authors":"Rina Takano , Rika Uesugi , Daichi Iida , Prof. Dr. Takayuki Ishida","doi":"10.1002/ajoc.202500049","DOIUrl":"10.1002/ajoc.202500049","url":null,"abstract":"<div><div>Three polymorphs of the title compound were found, showing a head‐to‐tail (N−O)<sub>2</sub> four‐membered ring. The α and β phases underwent a reversible structural phase transition across ca. 140 K, while the γ phase was independent. The interatomic O ⋅ ⋅ ⋅ N distances are 79–81 % of the sum of the van der Waals radii, consistent with the diamagnetic properties observed in the magnetic and ESR studies for the α phase. A thermally accessible zero‐field splitting pattern was recorded in solid‐state ESR, and applying a singlet‐triplet (ST) model afforded 2<em>J</em><sub>obs</sub>/<em>k</em><sub>B</sub>=−1.87(8)×10<sup>3</sup> K (<em>H</em>=−2<em>JS</em><sub>1</sub> ⋅ <em>S</em><sub>2</sub>). The SQUID results showed 2<em>J</em><sub>obs</sub>/<em>k</em><sub>B</sub>=–2.159(5)×10<sup>3</sup> K. Thanks to the introduction of two <em>tert</em>‐butyl groups on the naphthalene core, the generation of triplet species is reversible below 430 K. The residual electron density map from the crystallographic data and the QTAIM analysis indicate a four‐center two‐electron σ‐bond nature in (N−O)<sub>2</sub>. Two DFT‐optimized structures were given, featuring 2<em>J</em><sub>calc</sub>/<em>k</em><sub>B</sub>=−8864 K as a covalent model and −974 K as a biradical model. Thus, we can propose a mechanism involving two‐step equilibria; a chemical equilibrium between the covalent and biradical forms and a subsequent spin equilibrium between the S and T states in a biradical.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 5","pages":"Article e202500049"},"PeriodicalIF":2.8,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144072556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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(II)‐Catalyzed Tandem Intramolecular Oxidative Heck Reaction/C−H Arylation Sequence: One‐Pot Synthesis of 3‐Nitro‐2‐Aryl‐Indoles Pd（II）催化串联分子内氧化Heck反应/C - H芳基化序列：一锅合成3 -硝基- 2 -芳基-吲哚

IF 2.8 4区化学

Asian Journal of Organic Chemistry Pub Date : 2025-05-01 DOI: 10.1002/ajoc.202400692

Mohit K Tiwari , Muskan , Parthasarathi Das

{"title":"Pd(II)‐Catalyzed Tandem Intramolecular Oxidative Heck Reaction/C−H Arylation Sequence: One‐Pot Synthesis of 3‐Nitro‐2‐Aryl‐Indoles","authors":"Mohit K Tiwari , Muskan , Parthasarathi Das","doi":"10.1002/ajoc.202400692","DOIUrl":"10.1002/ajoc.202400692","url":null,"abstract":"<div><div>The present article describes a Pd(II)‐catalyzed cascade methodology that proceeds in a one‐step sequence <em>via</em> intramolecular oxidative Heck‐type C−C coupling and NO<sub>2</sub>‐directed selective C‐2 arylation of <em>in‐situ</em> formed 3‐nitroindoles with haloarenes. Importantly, this highly efficient and atom‐economical cascade protocol utilizes the same catalyst system and affords a diverse library of privileged C‐2‐aryl‐nitroindole scaffolds (<strong>5 a</strong>–<strong>5 aa</strong>) in a single step with good to excellent yields. Mechanistic investigations, including radical trapping, control, competition experiments and studies on the effects of EDGs and EWGs, strongly suggest the involvement of σ‐bond metathesis or a base accelerated proton abstraction, followed by the formation of a key intermediate <em>i. e</em>., a highly reactive Ar‐Pd−C‐2‐nitroindole complex, which further signifies the vital role of the NO<sub>2</sub> group in leading the efficiency and regioselectivity of the protocol. In addition, this cascade protocol is applicable in the ‘one pot’ synthesis of architecturally complex C‐5 functionalized (−F/‐Cl/‐Me/‐OMe) C‐2‐aryl‐nitroindoles and offers great potential in terms of biological and pharmaceutical fields.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 5","pages":"Article e202400692"},"PeriodicalIF":2.8,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144072566","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Synthesis of Five‐Membered Heterocycle Fused Quinazolinone Via Buchwald–Hartwig Cross Coupling Reaction Buchwald-Hartwig交叉偶联反应合成五元杂环熔融喹唑啉酮

IF 2.8 4区化学

Asian Journal of Organic Chemistry Pub Date : 2025-05-01 DOI: 10.1002/ajoc.202400795

Jimin Moon , Hyojin Lee , Taeho Lee

引用次数: 0

Divergent Behavior of β‐Carbonyl‐Substituted 1H‐Benzo[f]chromenes Under Henry Reaction Conditions β -羰基取代1H -苯并[f]铬在Henry反应条件下的发散行为

IF 2.8 4区化学

Asian Journal of Organic Chemistry Pub Date : 2025-05-01 DOI: 10.1002/ajoc.202400680

Kirill S. Korzhenko , Dmitry V. Osipov , Aleksandra S. Chechulina , Pavel E. Krasnikov , Oleg P. Demidov , Vitaly A. Osyanin

引用次数: 0

Rh(III)‐Catalyzed Regioselective [3+2]‐Annulation of Indoles with 1,3‐Enynes to Access 3H‐pyrrolo[1,2‐a]indol‐3‐ones Rh（III）‐催化区域选择性[3+2]‐吲哚与1,3‐炔环化以获得3H‐吡咯[1,2‐a]吲哚‐3‐酮

IF 2.8 4区化学

Asian Journal of Organic Chemistry Pub Date : 2025-05-01 DOI: 10.1002/ajoc.202400810

Sanjeev Kumar , Pradeep Girase , Sayali Pradeep Jadhav , Bhargav Desai , Dr. Togati Naveen , Vinaykumar Kanchupalli

引用次数: 0

Copper‐Catalyzed Synthesis of C‐2 Substituted Indolin‐3‐Ones and Indolin‐3‐One [4+2] Cycloadducts Through Azide‐Tethered Iodonium Ylides 铜催化叠氮化物系缚碘化物合成C - 2取代吲哚啉- 3 -酮和吲哚啉- 3 -酮[4+2]环加合物

IF 2.8 4区化学

Asian Journal of Organic Chemistry Pub Date : 2025-05-01 DOI: 10.1002/ajoc.202400612

Israel Najar Guerrero , Zinah Al‐Khateeb , Prof. F. G. West

引用次数: 0

Design of Supramolecular Tectons via Intramolecular S/Se⋅⋅⋅ONO2 Chalcogen Bonding 基于分子内S/Se⋅⋅⋅ONO2硫键的超分子结构设计

IF 2.8 4区化学

Asian Journal of Organic Chemistry Pub Date : 2025-05-01 DOI: 10.1002/ajoc.202500088

Artem V. Semenov , Eugene A. Katlenok , Alexey M. Starosotnikov , Maxim A. Bastrakov , Mikhail E. Minyaev , Lev E. Zelenkov , Anton A. Shetnev , Alexander V. Sapegin , Vadim P. Boyarskiy , Sergey V. Baykov

{"title":"Design of Supramolecular Tectons via Intramolecular S/Se⋅⋅⋅ONO2 Chalcogen Bonding","authors":"Artem V. Semenov , Eugene A. Katlenok , Alexey M. Starosotnikov , Maxim A. Bastrakov , Mikhail E. Minyaev , Lev E. Zelenkov , Anton A. Shetnev , Alexander V. Sapegin , Vadim P. Boyarskiy , Sergey V. Baykov","doi":"10.1002/ajoc.202500088","DOIUrl":"10.1002/ajoc.202500088","url":null,"abstract":"<div><div>A series of 2‐nitrochalcogenocyanato(hetero)arenes were synthesized by the reaction of 2‐nitrohalo(hetero)arenes with potassium thio‐ or selenocyanate. These compounds were characterized by NMR spectroscopy, high‐resolution mass spectrometry, and X‐ray crystallography. In the obtained crystal structures, strong intramolecular Ch⋅⋅⋅O<sub>NO2</sub> (Ch=S, Se) chalcogen bonds between the chalcogen atom of the chalcogenocyanate moiety and the nitro group were revealed. These interactions prevent rotation of the nitro group, and thus stabilize the obtained 2‐nitrochalcogenocyanato(hetero)arenes in a distorted planar geometry. In addition, intermolecular Ch⋅⋅⋅N chalcogen bonds were observed in some structures. Both intra‐ and intermolecular interactions were studied using methods based on first‐principles and DFT approaches (e. g. QTAIM, IGMH, ELF, NBO). Two of the synthesized chalcogenocyanates namely, 4‐nitro‐5‐thiocyanatophthalonitrile (<strong>2a</strong>) and 4‐nitro‐5‐selenocyanatophthalonitrile (<strong>2b</strong>) were identified as promising supramolecular tectons for cocrystallizations with aromatic hydrocarbons, and four new cocrystals (<strong>2 a⋅</strong>PhMe, <strong>2 a⋅</strong><em>o</em>‐XylH, <strong>2 a⋅</strong><em>p</em>‐XylH, and <strong>2 b⋅</strong>1.5(<em>p</em>‐XylH)) were obtained. X‐ray diffraction studies of these cocrystals demonstrated that in all cases molecules of the phthalonitrile (<strong>2 a</strong> or <strong>2 b</strong>) and the corresponding hydrocarbon are packed into infinity columnar stacks via π⋅⋅⋅π interactions, whereas intermolecular Ch⋅⋅⋅O/N ChBs bound them to form the final supramolecular architecture.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 5","pages":"Article e202500088"},"PeriodicalIF":2.8,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144072539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Dehydrogenative Coupling Reaction for the Synthesis of 5‐ and 6‐Heterocyclic Derivatives Catalyzed by Earth‐Abundant Metal‐Based Complexes 稀土金属基配合物催化合成5 -和6 -杂环衍生物的脱氢偶联反应

IF 2.8 4区化学

Asian Journal of Organic Chemistry Pub Date : 2025-05-01 DOI: 10.1002/ajoc.202400728

Dr. Nicolas Joly , Clara Mauclaire , Dr. Sylvain Gaillard , Dr. Albert Poater , Prof. Dr. Jean‐Luc Renaud

{"title":"Dehydrogenative Coupling Reaction for the Synthesis of 5‐ and 6‐Heterocyclic Derivatives Catalyzed by Earth‐Abundant Metal‐Based Complexes","authors":"Dr. Nicolas Joly , Clara Mauclaire , Dr. Sylvain Gaillard , Dr. Albert Poater , Prof. Dr. Jean‐Luc Renaud","doi":"10.1002/ajoc.202400728","DOIUrl":"10.1002/ajoc.202400728","url":null,"abstract":"<div><div>Heterocycle synthesis is an intense research area due to their significant importance in pharmaceutical, material chemistry and fine synthesis. Key innovations include transition metal‐based‐catalyzed heterocyclic derivatives synthesis, which facilitates diverse structural modifications, enhances selectivities and efficiency. The necessity to develop more greener technologies for the construction of new C−C and C−N bonds has strived chemists to re‐design their synthetic strategy plan and to introduce abundant starting materials. Among these new transformations, acceptorless dehydrogenative coupling (ADC) reactions have received increased attention thanks to their atom‐economy, the use of alcohols as pro‐electrophiles and the formation of water and hydrogen gas as only by‐products. These methods exemplify the interplay between traditional and cutting‐edge techniques, providing a robust synthetic toolkit to address the growing demand for biologically relevant compounds with tailored functionalities. This review will focus on the acceptorless dehydrogenative coupling methodologies for the synthesis of nitrogen‐containing 5‐ and 6‐membered heterocyclic derivatives (such as pyrroles, pyrimidines, quinazolines, and quinoxalines) in the presence of 3d‐metal complexes. The state of the art of the ADC process underscores the continuous evolution of synthetic strategies and emphases its importance in creating valuable and structurally diverse compounds, ensuring their centrality in both academic and pharmaceutical research.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 5","pages":"Article e202400728"},"PeriodicalIF":2.8,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144072545","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Möbius‐Aromaticity and Antiaromaticity Driven Nucleophilic Substitution Reactions in Cycloheptatrienide Zwitterions with a Twisted Cycloheptatetraene Intermediate Möbius‐扭曲环七烯中间体的芳构性和反芳构性驱动的亲核取代反应

IF 2.8 4区化学

Asian Journal of Organic Chemistry Pub Date : 2025-05-01 DOI: 10.1002/ajoc.202500119

Dr. Rinat F. Salikov , Alena D. Sokolova , Dr. Dmitry N. Platonov , Alexander Yu. Belyy , Michael D. Khitrov , Prof. Dr. Yury V. Tomilov

{"title":"Möbius‐Aromaticity and Antiaromaticity Driven Nucleophilic Substitution Reactions in Cycloheptatrienide Zwitterions with a Twisted Cycloheptatetraene Intermediate","authors":"Dr. Rinat F. Salikov , Alena D. Sokolova , Dr. Dmitry N. Platonov , Alexander Yu. Belyy , Michael D. Khitrov , Prof. Dr. Yury V. Tomilov","doi":"10.1002/ajoc.202500119","DOIUrl":"10.1002/ajoc.202500119","url":null,"abstract":"<div><div>Pyridinium and phosphonium zwitterions featuring a cycloheptatrienide‐anion moiety are introduced into antiaromatic nucleophilic substitution reactions. The transformations afford other zwitterions, cycloheptatrienes or cycloheptatrienide salts. The initial reaction stage involves an elimination of pyridine or triphenylphosphine to form a Möbius‐aromatic cycloheptatetraene intermediate. The aromatic stabilization energy in parent cycloheptatetraene was estimated at 6–7 kcal/mol, an important value in terms of reaction rates. An anisotropy of the induced current density diagram illustrated the diatropic ring current confirming the aromaticity of the intermediate and an analysis of NICS values for the initial reaction step revealed a transition from a slightly antiaromatic to a moderately aromatic species. Therefore, these reactions are uniquely driven by both the relief of antiaromaticity and the acquisition of Möbius aromaticity.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 5","pages":"Article e202500119"},"PeriodicalIF":2.8,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144072675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Copper‐Catalyzed Synthesis of Benzofuro[3,2‐b]Indole Frame Work via Intramolecular Oxidative C−H Bond Amination 铜催化分子内氧化C - H键胺化合成苯并呋喃[3,2 - b]吲哚骨架

IF 2.8 4区化学

Asian Journal of Organic Chemistry Pub Date : 2025-05-01 DOI: 10.1002/ajoc.202400702

Peramalla Edukondalu , Nidhi Ravi , Raghavender Matta , Gugulothu Kishan , Dr. K. Shiva Kumar

引用次数: 0