Organic chemistry frontiers : an international journal of organic chemistry最新文献_第5页

A cross-shaped organic framework: a multi-functional template arranging chromophores† 十字形有机骨架；一种排列发色团的多功能模板

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-01-08 DOI: 10.1039/d4qo01808g

Camiel C. E. Kroonen , Adriano D'Addio , Allesandro Prescimone , Daniel Häussinger , Marcel Mayor

{"title":"A cross-shaped organic framework: a multi-functional template arranging chromophores†","authors":"Camiel C. E. Kroonen , Adriano D'Addio , Allesandro Prescimone , Daniel Häussinger , Marcel Mayor","doi":"10.1039/d4qo01808g","DOIUrl":"10.1039/d4qo01808g","url":null,"abstract":"<div><div>This work explores the use of a cross-shaped organic framework that is used as a template for the investigation of multi-functionalized chromophores. We report the design and synthesis of a universal cross-shaped building block bearing two bromines and two iodines on its peripheral positions. The template can be synthesized on a gram scale in a five-step reaction comprising an oxidative homo-coupling macro-cyclization. The formed scaffold was selectively functionalized <em>via</em> Suzuki cross-coupling reactions with methoxynaphthalene, naphthalimide and BODIPY derivatives, yielding a library of cross-shaped and chromophore-decorated model compounds, all of which were fully characterized. The formed racemic bis- and tetra-substituted crosses were resolved <em>via</em> chiral stationary phase HPLC, and assignment of the enantiomers was done <em>via</em> comparison of experimental and simulated electronic circular dichroism spectra as well as enantiomer single-crystal analysis. Additionally, the hybrid naphthalimide/BODIPY chromophore was found to be acting as an intramolecular Förster energy resonance transfer pair, which was investigated in more detail. With this easy-to-functionalize universal building block, we believe it might prove to be useful in the study of different sets of chromophores.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 5","pages":"Pages 1399-1408"},"PeriodicalIF":0.0,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qo/d4qo01808g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763909","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Modular synthesis of β-oxygen-containing sulfones from alkenes through hexatungstate-catalyzed cascade hydroxysulfenylation/selective oxidation† 六通酸催化级联羟基磺酰化/选择性氧化烯烃模块化合成β-含氧砜

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-01-08 DOI: 10.1039/d4qo02151g

Jiaoxiong Li , Zhibin Zhou , Xianghua Zeng , Yongge Wei

{"title":"Modular synthesis of β-oxygen-containing sulfones from alkenes through hexatungstate-catalyzed cascade hydroxysulfenylation/selective oxidation†","authors":"Jiaoxiong Li , Zhibin Zhou , Xianghua Zeng , Yongge Wei","doi":"10.1039/d4qo02151g","DOIUrl":"10.1039/d4qo02151g","url":null,"abstract":"<div><div>β-Oxygen-containing sulfones are versatile building blocks in pharmaceuticals and the chemical industry. Despite notable advances in the reported methods, a sustainable and general catalytic method for preparing β-oxygen-containing sulfones remains elusive, due to the inherent reactivity disparities and notorious metal-catalyst-poisoning capability of sulfur nucleophiles. Here, we present a distinct multifunctional hexatungstate catalytic strategy for the synthesis of β-hydroxy sulfones and β-keto sulfones through a sequential hydroxysulfenylation of alkenes/selective oxidation process, utilizing a commerically available thiol and green hydrogen peroxide as the ‘oxy-sulfonylation reagent’. This method not only offers a practical route for delivering functionalized sulfones from readily available chemicals but is also sufficiently versatile to achieve late-stage oxysulfonylation of complex substrates and concise syntheses of bioactive molecules. Moreover, this modular methodology features a new mechanism, water as the sole byproduct, and mild reaction conditions free of hydroperoxide reductant.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 5","pages":"Pages 1444-1451"},"PeriodicalIF":0.0,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820723","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cation radicals, borenium cations, and a dication from the oxidation of B-tolyl BIII subporphyrins† b - toyl - BIII亚卟啉氧化的阳离子自由基，硼离子和指示

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-01-08 DOI: 10.1039/d4qo02291b

Zixuan Xie , Xiaoheng Ji , Xu Zeng , Daiki Shimizu , Takayuki Tanaka , Yutao Rao , Mingbo Zhou , Ling Xu , Atsuhiro Osuka , Jianxin Song

{"title":"Cation radicals, borenium cations, and a dication from the oxidation of B-tolyl BIII subporphyrins†","authors":"Zixuan Xie , Xiaoheng Ji , Xu Zeng , Daiki Shimizu , Takayuki Tanaka , Yutao Rao , Mingbo Zhou , Ling Xu , Atsuhiro Osuka , Jianxin Song","doi":"10.1039/d4qo02291b","DOIUrl":"10.1039/d4qo02291b","url":null,"abstract":"<div><div>Oxidation of B-tolyl B<sup>III</sup> 5,10,15-tritolylsubporphyrin with tris(4-bromophenyl)ammoniumyl hexachloroantimonate gave its cation radical instantaneously, which slowly dissociated to give B<sup>III</sup> subporphyrin borenium hexachloroantimonate in 89% yield after stirring overnight. This is a much more convenient method for the synthesis of B<sup>III</sup> borenium cations than the previous synthesis with [Et<sub>3</sub>Si]<sup>+</sup>[CH<sub>6</sub>B<sub>11</sub>Br<sub>6</sub>]<sup>−</sup>. Oxidants such as tris(4-bromophenyl)ammonium tetrakis(perfluorophenyl)borate and AgSbF<sub>6</sub> can be used for the synthesis of the borenium cation. Oxidation of B-tolyl B<sup>III</sup> 5,10,15-trianisylsubporphyrin with AgSbF<sub>6</sub> gave a cation radical that was stable at room temperature but dissociated to give the corresponding borenium cation upon refluxing in CH<sub>2</sub>Cl<sub>2</sub>, while the B-tolyl B<sup>III</sup> 5,10,15-tris(4-dibutylaminophenyl)subporphyrin was oxidized to give a cation radical that was easily oxidized to afford a quinonoidal dication. Oxidation of B-tolyl B<sup>III</sup> β-hexaethyl-5,10,15-tri(4-diethylaminophenyl)subporphyrin with AgSbF<sub>6</sub> gave a borenium cation instantaneously. As such, the reactivities of the cation radicals depend on the peripheral substituents.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 5","pages":"Pages 1565-1571"},"PeriodicalIF":0.0,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ball-milling and piezoelectric materials enabled radical trifluoromethylation of enamides and acrylamides† 球磨和压电材料使酰胺和丙烯酰胺的自由基三氟甲基化成为可能

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-01-08 DOI: 10.1039/d4qo01911c

Vitalii Solomin , Matthias Liard , Philippe Jubault , Thomas Castanheiro

{"title":"Ball-milling and piezoelectric materials enabled radical trifluoromethylation of enamides and acrylamides†","authors":"Vitalii Solomin , Matthias Liard , Philippe Jubault , Thomas Castanheiro","doi":"10.1039/d4qo01911c","DOIUrl":"10.1039/d4qo01911c","url":null,"abstract":"<div><div>A mechanochemical radical direct C(sp<sup>2</sup>)–H trifluoromethylation of enamide derivatives was developed using Togni II reagent. Under mechanochemical compression, the use of 0.5 to 1.0 equivalents of piezoelectric materials enabled the solid-state formation of the key CF<sub>3</sub> radical intermediate in mild and sustainable conditions. The use of 0.5 equivalents of piezoelectric materials proved to be just as efficient. The protocol showed a general efficiency and tolerance to multiple functional groups, accessing trifluoromethylated enamides with yields of up to 88% and full stereoselectivity. The reaction conditions were applied to acrylamide substrates, enabling synthesis of trifluoromethylated oxindole derivatives through a radical cascade cyclization initiated from addition of CF<sub>3</sub> radical onto electron-poor C–C double bonds. Radical quenching experiments highlighted a radical mechanism, and control experiments showcased the crucial need to use of piezoelectric materials/ball-milling system.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 5","pages":"Pages 1467-1473"},"PeriodicalIF":0.0,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Electromagnetic milling promoted mechanochemical copper-catalyzed C–O coupling reaction for diaryl ether formation† 电磁铣削促进铜催化的机械化学C-O偶联反应生成二芳基醚

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-01-08 DOI: 10.1039/d4qo01909a

Zhaoxuan Zeng , Zhe Tian , Zhihan Zhang , Hongzhen Sun , Qing Liu , Lizhi Zhang , Fachao Yan , Zengdian Zhao , Hui Liu

引用次数: 0

Metal-free synthesis of carboxamides via the Lossen rearrangement† 通过Lossen重排法无金属合成羧酰胺

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-01-08 DOI: 10.1039/d4qo02155j

Chong Li , Yi-Fei Liu , Wei Yang , Lian-Jie Zhao , Lin-Yuan Song , Yu-Shuang Deng , Ke-Yu Mou , Jing-Wen Wang , Sheng Cao , Feng Li

引用次数: 0

Intermolecular amination of ethyl benzo ylacetate via photocatalytic nitrene transfer reactions† 光催化硝基转移反应中乙酸苯乙酯的分子间胺化反应

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-01-08 DOI: 10.1039/d4qo02194k

Yujing Guo , Yifan Guo , Luyao Ding , Linlin Shi , Xinqi Hao , Rene M. Koenigs

引用次数: 0

Recent advances in enantioselective construction of C–N bonds involving radical intermediates 含自由基中间体的C-N键对映选择性构建研究进展

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-01-08 DOI: 10.1039/d4qo02268h

Jiaqiong Sun , Guangfan Zheng , Ge Zhang , Yan Li , Qian Zhang

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Multichromophoric perylene–iridium triad as a homogeneous photocatalyst for the efficient synthesis of tetrahydroquinoline derivatives† 四氢喹啉衍生物高效合成的多色苝铱三元均相光催化剂

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-01-08 DOI: 10.1039/d4qo02269f

Anita Kumari , Sanchita Sengupta

引用次数: 0

Cobalt-catalyzed regioselective diazidation of 1-aryl-1,3-dienes enabled by a single electron transfer/radical addition/group transfer relay process† 通过单电子转移/自由基加成/基团转移接力过程实现钴催化1 -芳基-1,3-二烯的区域选择性重氮化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-01-08 DOI: 10.1039/d4qo02180k

Chi-Fan Zhu , Jun-Ju Mai , Xiao-Jing Li , Mingyuan Shi , Xiasen Dong , Huinan Fu , Mei-Hua Shen , Hua-Dong Xu

引用次数: 0