Zeng Han , Lianhui Wang , Yuanqi Luo , Xiuling Cui
{"title":"Photocatalytic intermolecular [2 + 2] cycloaddition/dearomatization of indoles: easy access to cyclobutane-fused indolines†","authors":"Zeng Han , Lianhui Wang , Yuanqi Luo , Xiuling Cui","doi":"10.1039/d4qo02302a","DOIUrl":"10.1039/d4qo02302a","url":null,"abstract":"<div><div>Visible-light-promoted [2 + 2] cycloaddition/dearomatization of aromatic compounds is an efficient strategy for the synthesis of three-dimensional rigid four-membered rings to realize the modification of organic molecules, which boasts great potential and prospects in developing first-class drugs. Herein, cyclobutane-fused indolines were successfully synthesized <em>via</em> a photocatalytic intermolecular [2 + 2] cycloaddition/dearomatization reaction with olefins. This reaction exhibited excellent regio- and stereoselectivity (>20 : 1 dr) and high atom- and step-economy, and is characterized by mild and green reaction conditions, simple operation, and a wide range of substrate applicability. The mechanistic control exploration suggested that the [2 + 2] cycloaddition reaction was initiated by the triplet–triplet energy transfer paradigm.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 10","pages":"Pages 3177-3183"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538483","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}
Biao Cheng , Jialong Xv , Xiang Ren , Yuanyuan Li , Xiaoming Ji , Zhan Lu
{"title":"Highly efficient low-valence tungsten-catalyzed deoxygenative reduction of tertiary amides to amines with pinacolborane†","authors":"Biao Cheng , Jialong Xv , Xiang Ren , Yuanyuan Li , Xiaoming Ji , Zhan Lu","doi":"10.1039/d4qo02340d","DOIUrl":"10.1039/d4qo02340d","url":null,"abstract":"<div><div>A highly efficient low-valence tungsten-catalyzed deoxygenative reduction of tertiary amides to amines with pinacolborane (HBPin) is developed. This protocol uses commercially available W(CO)<sub>6</sub> as a catalyst in a solution of hexane under the irradiation of visible light without other additives, and the TON is up to 2000.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 10","pages":"Pages 3306-3312"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582959","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}
Jun Liu , Jingjing Bi , Yuxin Cui , Minhao Chen , Chuanfang Zhao , Wenting Li , Aishuang Zhan , Yuguo Du
{"title":"Total synthesis and structure revision of gonioheptenolactone†","authors":"Jun Liu , Jingjing Bi , Yuxin Cui , Minhao Chen , Chuanfang Zhao , Wenting Li , Aishuang Zhan , Yuguo Du","doi":"10.1039/d5qo00088b","DOIUrl":"10.1039/d5qo00088b","url":null,"abstract":"<div><div>We report the first total synthesis and structure revision of the cytotoxic styryllactone gonioheptenolactone. The synthesis features a highly stereoselective epoxide formation followed by an intramolecular, regioselective nucleophilic epoxide-opening reaction to construct the key tetrahydrofuran skeleton. Our findings reveal that the originally proposed structure of gonioheptenolactone as an unsaturated eight-membered lactone is incorrect; the actual structure is revised to tetrahydrofuryl acrylate. The synthesized natural products, gonioheptenolactone and isoaltholactone, were evaluated for their <em>in vitro</em> antiproliferative activity against a panel of human tumor cell lines, providing further biological insights.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 12","pages":"Pages 3665-3672"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640311","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}
Alexandre Simon , Virgile Rouffeteau , Camilla Acconcia , Sylvestre P. J. T. Bachollet , Jérémy Forté , Mariateresa Giustiniano , Laurence Grimaud , Maxime R. Vitale
{"title":"Pseudo-4-component photoredox-catalyzed alkylative amidination/carbamoylation of styrenes with isocyanides and redox-active esters†","authors":"Alexandre Simon , Virgile Rouffeteau , Camilla Acconcia , Sylvestre P. J. T. Bachollet , Jérémy Forté , Mariateresa Giustiniano , Laurence Grimaud , Maxime R. Vitale","doi":"10.1039/d5qo00352k","DOIUrl":"10.1039/d5qo00352k","url":null,"abstract":"<div><div>We report a photoredox-catalyzed pseudo-four-component process for the alkylative amidination of styrenes using isocyanides and redox-active esters (RAEs). This redox-neutral radical-polar crossover reaction shows broad functional group tolerance. The RAE serves as both a radical and nucleophile source, with the initially released phthalimide anion reintegrated into the final product. The resulting amidines can be readily derivatized into amides, tetrazoles, nitriles, or aldehydes, enhancing the synthetic utility of this approach.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 12","pages":"Pages 3551-3557"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640307","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}
Chun-Hong Long , Hang Cai , Yuan Sun , Zhao-Nan Cai , Hong-Bo Qin
{"title":"Metal-free photoredox catalyzed formation of S–C–S and C–S bonds through coupling of diaryl sulfides/benzyl chlorides with dichloromethyl derivatives†","authors":"Chun-Hong Long , Hang Cai , Yuan Sun , Zhao-Nan Cai , Hong-Bo Qin","doi":"10.1039/d5qo00218d","DOIUrl":"10.1039/d5qo00218d","url":null,"abstract":"<div><div>A metal-free photoredox method for the synthesis of S–C–S and C–S bonds has been developed, offering a sustainable and efficient approach for producing diaryl dithioacetals and aryl benzyl sulfides. This method employs 4CzIPN as a photocatalyst and DIPEA as a base, enabling the formation of sulfur and carbon radicals through single electron transfer (SET) and halogen atom transfer (XAT) mechanisms. This protocol features a broad substrate scope, moderate to excellent yields, and scalability under solvent-free conditions or using water as a green solvent. Gram-scale synthesis and sunlight-driven reactions demonstrate its potential for industrial applications. Mechanistic studies, including fluorescence quenching and radical trapping experiments, have confirmed that DIPEA serves as a quencher of the excited state of 4CzIPN and that the reaction involves a radical pathway. This environmentally friendly strategy provides a versatile platform for constructing valuable sulfur-containing compounds with applications in synthetic chemistry and drug development.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 10","pages":"Pages 3264-3270"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143589911","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}
Yanchuang Zhao , Yuenian Xu , Han Qian , Aman Ullah , Shao-Fei Ni , Ying Bai , Xinxin Shao
{"title":"Discovery of zinc-bound dithiolates for C(sp3)–S couplings of alkyl iodides: a radical solution to nucleophilic substitution†","authors":"Yanchuang Zhao , Yuenian Xu , Han Qian , Aman Ullah , Shao-Fei Ni , Ying Bai , Xinxin Shao","doi":"10.1039/d5qo00298b","DOIUrl":"10.1039/d5qo00298b","url":null,"abstract":"<div><div>The nucleophilic (thio)etherification of haloalkanes with O/S nucleophiles, known as Williamson (thio)etherification, is a prominent approach for synthesizing alkyl (thio)ethers. However, the reaction generally requires an elevated temperature and is primarily applicable to primary alkyl halides. Here, we develop a new class of bench-stable zinc dithiolates as thiolating reagents that oriented the radical functionalization of various alkyl iodides at room temperature to address the long-standing challenges associated with nucleophilic substitution. The base-free reactions proceed with excellent chemo-selectivity and broad functional group tolerance. Mechanistic studies reveal that these efficient C(sp<sup>3</sup>)–S couplings proceed through a synergistic single electron transfer (SET) of zinc dithiolates with diazonium salts and subsequent halogen atom transfer (XAT) between aryl radicals and alkyl iodides.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 12","pages":"Pages 3649-3657"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618286","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}
Yu-Zhao Wang , Di-Di Tang , Han-Yue Zhang , Xiao-Yue Ma , De-Hua Xing , Chenjiang Liu , Yu Xia , Yan Li
{"title":"Visible-light-induced three-component radical cascade 1,2-dialkylation of alkenes to access alcohols†","authors":"Yu-Zhao Wang , Di-Di Tang , Han-Yue Zhang , Xiao-Yue Ma , De-Hua Xing , Chenjiang Liu , Yu Xia , Yan Li","doi":"10.1039/d5qo00080g","DOIUrl":"10.1039/d5qo00080g","url":null,"abstract":"<div><div>Visible-light-mediated 1,2-dicarbofunctionalization of alkenes provides a powerful tool for the synthesis of structurally complicated and diverse molecules from simple precursors in one step. In this work, photo-catalyzed three-component 1,2-alkylation of alkenes with alkylboronic pinacol esters (APEs) and aldehydes has been accomplished. This transition-metal-free protocol provided a clean and efficient way to access secondary alcohols, with wide substrate scope compatibility and good functional group tolerance, and it allowed a variety of alkenes, APEs and aldehydes to be transformed to the desired products in moderate to good yields under metal-free conditions. Mechanism studies disclosed that this transformation may involve a radical addition and radical–radical cross-coupling process.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 9","pages":"Pages 3035-3040"},"PeriodicalIF":0.0,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143470685","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}
Man Miao , Zhenjie Qi , Fengkai Sun , Hui Yuan , Xiao-Bing Lan , Ping Zheng , Jian-Qiang Yu , Xiaoli Guo , Jian Zhang , Zhenyu An
{"title":"Rh(iii)-catalyzed domino annulation strategy to synthesize benzo[c]naphthyridinones from 3-diazooxindoles and isoxazolones†","authors":"Man Miao , Zhenjie Qi , Fengkai Sun , Hui Yuan , Xiao-Bing Lan , Ping Zheng , Jian-Qiang Yu , Xiaoli Guo , Jian Zhang , Zhenyu An","doi":"10.1039/d5qo00079c","DOIUrl":"10.1039/d5qo00079c","url":null,"abstract":"<div><div>A convenient methodology for the synthesis of benzo[<em>c</em>]naphthyridinone derivatives was developed <em>via</em> a Rh(<span>iii</span>)-catalyzed and Cu(<span>i</span>)-oxidized annulation of 3-diazooxindoles with 3-aryl-5-isoxazolones. This transformation involves the <em>in situ</em> generation of a tricyclic core through an unprecedented ring-expansion of 3-diazooxindoles with good functional group tolerance. Consecutive C–C and C–N bond formations and CO<sub>2</sub> elimination are the key steps for success, as demonstrated by detailed DFT studies.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 9","pages":"Pages 3058-3064"},"PeriodicalIF":0.0,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532620","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}
{"title":"Mechanism of formation of chiral allyl SCF3 compounds via selenium-catalyzed sulfenofunctionalization of allylboronic acids†","authors":"Wen-Jie Wei , Kalman J. Szabo , Fahmi Himo","doi":"10.1039/d4qo02170c","DOIUrl":"10.1039/d4qo02170c","url":null,"abstract":"<div><div>The detailed reaction mechanism of diphenyl selenide-catalyzed sulfenofunctionalization of chiral α-CF<sub>3</sub> allylboronic acids is investigated by means of density functional theory calculations. It is demonstrated that the reaction starts with the transfer of the SCF<sub>3</sub> group from the (PhSO<sub>2</sub>)<sub>2</sub>NSCF<sub>3</sub> reagent to the Ph<sub>2</sub>Se catalyst, a process that is shown to be assisted by the presence of Tf<sub>2</sub>NH acid. After a proton transfer step, the SCF<sub>3</sub> group is transferred to the CC double bond of the substrate to generate a thiiranium ion. Concerted deborylative opening of the thiiranium ion yields then the final product. Several representative substrates are considered by the calculations, and the origins of the stereoselectivity of the reactions are analyzed by comparing the energies and geometries of the transition states leading to the different products.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 9","pages":"Pages 2994-3003"},"PeriodicalIF":0.0,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518313","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}
Liuzhou Gao , Linghui Meng , Yan Wen , Jingyi Hu , Yuxin Sun , Shenglong Wang , Guoqiang Wang , Yidong Wang
{"title":"t BuOK-mediated selective 1,2-silacarboxylation of arylalkenes with Si–B/Si–Si/Si–Li reagents and CO2†","authors":"Liuzhou Gao , Linghui Meng , Yan Wen , Jingyi Hu , Yuxin Sun , Shenglong Wang , Guoqiang Wang , Yidong Wang","doi":"10.1039/d4qo02261k","DOIUrl":"10.1039/d4qo02261k","url":null,"abstract":"<div><div>An operationally simple base-mediated silacarboxylation of arylalkenes has been developed to synthesize valuable β-silyl functionalized phenylacetic acid derivatives utilizing carbon dioxide and silanion reagents. The protocol is applicable to a diverse range of vinyl substrates including mono-, di-, and trisubstituted alkenes under mild conditions. Control experiments combined with DFT calculations reveal that the reaction starts with the nucleophilic addition of silanion species to alkenes, followed by direct trapping of the <em>in situ</em> formed benzylic carbanion with CO<sub>2</sub>, yielding the silacarboxylation products. Based on the mechanistic insight, the scope of silyl nucleophiles for this transformation can be extended to disilane (Si–Si) or silyl lithium (Si–Li) reagents. The relevance of this method for the synthesis of pharmaceutically relevant compounds further demonstrates its potential applications.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 9","pages":"Pages 2935-2945"},"PeriodicalIF":0.0,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143470689","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}