Pub Date : 2025-09-05Epub Date: 2025-06-18DOI: 10.1039/d5qo00670h
Meiling Ye , Hang Wang , Min Liao , Zeyu Tian , Zhongzhen Yang , Yong Wu
A visible-light-induced radical-polar crossover cyclization (RPCC) reaction between homoallylic substrates and sulfamate esters for the synthesis of γ-alkylated 1,1-disubstituted cyclopropanes via 1,6-HAT processes has been reported. This protocol displays mild and metal-free conditions, excellent functional group tolerance and a broad range of substrates. Furthermore, the potential synthetic potential of this transformation is demonstrated by scale-up reactions and synthetic applications.
{"title":"Radical-polar crossover cyclization: visible-light-induced synthesis of γ-alkylated 1,1-disubstituted cyclopropanes via 1,6-hydrogen atom transfer†","authors":"Meiling Ye , Hang Wang , Min Liao , Zeyu Tian , Zhongzhen Yang , Yong Wu","doi":"10.1039/d5qo00670h","DOIUrl":"10.1039/d5qo00670h","url":null,"abstract":"<div><div>A visible-light-induced radical-polar crossover cyclization (RPCC) reaction between homoallylic substrates and sulfamate esters for the synthesis of γ-alkylated 1,1-disubstituted cyclopropanes <em>via</em> 1,6-HAT processes has been reported. This protocol displays mild and metal-free conditions, excellent functional group tolerance and a broad range of substrates. Furthermore, the potential synthetic potential of this transformation is demonstrated by scale-up reactions and synthetic applications.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5553-5558"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341384","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}
Pub Date : 2025-09-05Epub Date: 2025-06-05DOI: 10.1039/d5qo00697j
Jiajun Zhao , Xiaolong Wang , Yan Cao , Jun Ying
A palladium-catalyzed cascade radical cyclization and C–H amination of 1,7-enynes with perfluoroalkyl iodides and hydroxylamine has been developed for the rapid construction of tricyclic quinolin-2(1H)-one scaffolds. The reaction proceeded smoothly to give a series of tricyclic quinolin-2(1H)-one derivatives in high yields. Notably, the late-stage modifications of various drugs were realized by using this method.
{"title":"Palladium-catalyzed cascade synthesis of tricyclic quinolin-2(1H)-ones from 1,7-enynes and hydroxylamines†","authors":"Jiajun Zhao , Xiaolong Wang , Yan Cao , Jun Ying","doi":"10.1039/d5qo00697j","DOIUrl":"10.1039/d5qo00697j","url":null,"abstract":"<div><div>A palladium-catalyzed cascade radical cyclization and C–H amination of 1,7-enynes with perfluoroalkyl iodides and hydroxylamine has been developed for the rapid construction of tricyclic quinolin-2(1<em>H</em>)-one scaffolds. The reaction proceeded smoothly to give a series of tricyclic quinolin-2(1<em>H</em>)-one derivatives in high yields. Notably, the late-stage modifications of various drugs were realized by using this method.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5467-5471"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219145","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}
Pub Date : 2025-09-05Epub Date: 2025-06-05DOI: 10.1039/d5qo00708a
Krzysztof Górski , Łukasz W. Ciszewski , Antoni Wrzosek , Adam Szewczyk , Andrzej L. Sobolewski , Daniel T. Gryko
A new straightforward methodology for the synthesis of phosphonium salts integrated with a π-conjugated scaffold has been developed using phosphine oxides. It is now possible to obtain cyclic phosphonium salts possessing up to eight conjugated rings and bearing e.g. pyrrole, thiophene, indole or benzofuran scaffolds from abundant and commercially available materials in high yields. An enticing feature of this general strategy is that this one-step procedure typically does not require chromatographic purification. Still greater synthetic possibilities are related to the fact that even demanding scaffolds such as azulene, pyrene or fluorene can be bridged with the phospholium subunit. Starting from 1,4-dihydropyrrolo[3,2-b]pyrrole, heretofore rarely observed ladder-type bis-phosphonium salts were effectively prepared. This strategy was also extended into the preparation of cyclic arsonium salt. The ability to form phosphonium salts possessing such manifold scaffolds translated into diverse photophysical properties ranging from non-fluorescent dyes to thiophene-derivatives emitting quantitatively in the blue region. Geometry change induced by light absorption has a predominant influence on the fate of the molecules’ excited state. It was shown, in analogy to previous results, that cyclic tetraarylphosphonium salts migrate through the membrane of living cells to localize in the mitochondria similarly to the well-known triarylphosphonium salts.
{"title":"An efficient method for the synthesis of π-expanded phosphonium salts†","authors":"Krzysztof Górski , Łukasz W. Ciszewski , Antoni Wrzosek , Adam Szewczyk , Andrzej L. Sobolewski , Daniel T. Gryko","doi":"10.1039/d5qo00708a","DOIUrl":"10.1039/d5qo00708a","url":null,"abstract":"<div><div>A new straightforward methodology for the synthesis of phosphonium salts integrated with a π-conjugated scaffold has been developed using phosphine oxides. It is now possible to obtain cyclic phosphonium salts possessing up to eight conjugated rings and bearing <em>e.g.</em> pyrrole, thiophene, indole or benzofuran scaffolds from abundant and commercially available materials in high yields. An enticing feature of this general strategy is that this one-step procedure typically does not require chromatographic purification. Still greater synthetic possibilities are related to the fact that even demanding scaffolds such as azulene, pyrene or fluorene can be bridged with the phospholium subunit. Starting from 1,4-dihydropyrrolo[3,2-<em>b</em>]pyrrole, heretofore rarely observed ladder-type bis-phosphonium salts were effectively prepared. This strategy was also extended into the preparation of cyclic arsonium salt. The ability to form phosphonium salts possessing such manifold scaffolds translated into diverse photophysical properties ranging from non-fluorescent dyes to thiophene-derivatives emitting quantitatively in the blue region. Geometry change induced by light absorption has a predominant influence on the fate of the molecules’ excited state. It was shown, in analogy to previous results, that cyclic tetraarylphosphonium salts migrate through the membrane of living cells to localize in the mitochondria similarly to the well-known triarylphosphonium salts.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5484-5495"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219154","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}
Susanta Patra , Arunava Sengupta , Parthasarathi Das
The palladium-catalyzed site-selective arylation of N-vinyl-7-azaindole (AI) derivatives using (hetero)iodoarenes is reported. While N-vinyl-7-azaindole displays moderate regioselectivity, predominantly favoring α-arylation, N-oxide activation (AINO) induces a complete switch to exclusive β-arylation with high E-selectivity. Control experiments and DFT studies support the mechanistic basis of this switch, which arises from the formation of distinct metallocyclic π-complexes: a five-membered complex for α-arylation and a six-membered complex for β-arylation. These findings highlight N-oxide activation as a powerful strategy to control regioselectivity in Heck-type arylations of N-vinyl-7-azaindoles. The transformation proceeds under ligand-free conditions and showcases broad substrate scope and excellent functional group tolerance.
{"title":"Site selective Heck arylation of N-vinyl-7-azaindole engineered by N-oxide activation: scope and mechanistic studies","authors":"Susanta Patra , Arunava Sengupta , Parthasarathi Das","doi":"10.1039/d5qo00976f","DOIUrl":"10.1039/d5qo00976f","url":null,"abstract":"<div><div>The palladium-catalyzed site-selective arylation of <em>N</em>-vinyl-7-azaindole (AI) derivatives using (hetero)iodoarenes is reported. While <em>N</em>-vinyl-7-azaindole displays moderate regioselectivity, predominantly favoring α-arylation, <em>N</em>-oxide activation (AINO) induces a complete switch to exclusive β-arylation with high <em>E</em>-selectivity. Control experiments and DFT studies support the mechanistic basis of this switch, which arises from the formation of distinct metallocyclic π-complexes: a five-membered complex for α-arylation and a six-membered complex for β-arylation. These findings highlight <em>N</em>-oxide activation as a powerful strategy to control regioselectivity in Heck-type arylations of <em>N</em>-vinyl-7-azaindoles. The transformation proceeds under ligand-free conditions and showcases broad substrate scope and excellent functional group tolerance.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5379-5386"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145002973","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}
Pub Date : 2025-09-05Epub Date: 2025-06-09DOI: 10.1039/d5qo00740b
Yongjing Dong , Yue Hu , Yiqing Wang , Liqun Jin , Yinjun Xie
The use of silicon reagents as catalysts has long been an attractive yet challenging goal due to difficulties in silicon catalyst regeneration. Herein, we report a novel silicon-catalyzed formal hydroformylation of alkynes with aldehydes to access α,β-unsaturated ketones with high efficiency under mild conditions. The success of this method relies on an innovative retro-Mukaiyama aldol reaction (RMAR)-driven silyl transfer strategy, which enables efficient regeneration of silicon catalysts. Preliminary mechanistic studies reveal the evolution of key silicon catalysts during this transformation. This protocol provides valuable insights for the design of new chemical transformations based on silicon catalysis.
{"title":"Retro-Mukaiyama aldol reaction-driven silicon catalysis†","authors":"Yongjing Dong , Yue Hu , Yiqing Wang , Liqun Jin , Yinjun Xie","doi":"10.1039/d5qo00740b","DOIUrl":"10.1039/d5qo00740b","url":null,"abstract":"<div><div>The use of silicon reagents as catalysts has long been an attractive yet challenging goal due to difficulties in silicon catalyst regeneration. Herein, we report a novel silicon-catalyzed formal hydroformylation of alkynes with aldehydes to access α,β-unsaturated ketones with high efficiency under mild conditions. The success of this method relies on an innovative retro-Mukaiyama aldol reaction (RMAR)-driven silyl transfer strategy, which enables efficient regeneration of silicon catalysts. Preliminary mechanistic studies reveal the evolution of key silicon catalysts during this transformation. This protocol provides valuable insights for the design of new chemical transformations based on silicon catalysis.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5540-5546"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238261","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}
Pub Date : 2025-09-05Epub Date: 2025-06-20DOI: 10.1039/d5qo00744e
Ying Tong , Jia-Yao Feng , Cuiyan Wu , Shi-Qing Zhang , Ming-Qi Yang , Sheng Du , Dong-Qing Yang , Keqi Tang , Chao Deng , Wen-Ting Wei
Two-component alkene coupling reactions serve as an efficient platform for the synthesis of complex molecular architectures. Leveraging the differences in activation energy barriers among carbon radical precursors and the polarity matching between radicals, this work reports the first example of radical 1,4-acylcyanoalkylation to synthesize challenging-to-access ζ-ketonitriles using two identical alkenes. In the metal-free system, 2-(tert-butylperoxy)-2-methylpropane (DTBP) respectively activates α-C–H bonds of aldehydes and alkyl nitriles to generate acyl and cyanoalkyl radicals. The reaction sequence involves selective radical addition of the acyl radical to two identical alkenes, followed by radical–radical coupling with the cyanoalkyl radical, thereby constructing three C–C bonds under simple conditions. Remarkably, when tertiary alkyl aldehydes are employed, decarbonylation preferentially occurs to form alkyl radicals, enabling 1,4-alkylcyanoalkylation of alkenes. Mechanistic studies and density functional theory (DFT) calculations reveal that the success of this 1,4-acylcyanoalkylation process is governed by both the preferential addition of acyl radicals to alkenes and the thermodynamic stability associated with the two-component alkene addition cascade.
{"title":"Radical 1,4-acylcyanoalkylation of alkenes for the synthesis of ζ-ketonitriles†","authors":"Ying Tong , Jia-Yao Feng , Cuiyan Wu , Shi-Qing Zhang , Ming-Qi Yang , Sheng Du , Dong-Qing Yang , Keqi Tang , Chao Deng , Wen-Ting Wei","doi":"10.1039/d5qo00744e","DOIUrl":"10.1039/d5qo00744e","url":null,"abstract":"<div><div>Two-component alkene coupling reactions serve as an efficient platform for the synthesis of complex molecular architectures. Leveraging the differences in activation energy barriers among carbon radical precursors and the polarity matching between radicals, this work reports the first example of radical 1,4-acylcyanoalkylation to synthesize challenging-to-access ζ-ketonitriles using two identical alkenes. In the metal-free system, 2-(<em>tert</em>-butylperoxy)-2-methylpropane (DTBP) respectively activates α-C–H bonds of aldehydes and alkyl nitriles to generate acyl and cyanoalkyl radicals. The reaction sequence involves selective radical addition of the acyl radical to two identical alkenes, followed by radical–radical coupling with the cyanoalkyl radical, thereby constructing three C–C bonds under simple conditions. Remarkably, when tertiary alkyl aldehydes are employed, decarbonylation preferentially occurs to form alkyl radicals, enabling 1,4-alkylcyanoalkylation of alkenes. Mechanistic studies and density functional theory (DFT) calculations reveal that the success of this 1,4-acylcyanoalkylation process is governed by both the preferential addition of acyl radicals to alkenes and the thermodynamic stability associated with the two-component alkene addition cascade.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5603-5609"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329487","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}
Pub Date : 2025-09-05Epub Date: 2025-06-03DOI: 10.1039/d5qo00551e
Ji-Hong Gu , Ni-Ping Li , Hao-Ting Lin , Ling-Na Dai , Min-Jing Cheng , Jian Hong , Yi-Yi Li , Jun-Shan Liu , Wen-Cai Ye , Lei Wang
Gelsepolycines A–F (), six oligomeric monoterpenoid indole alkaloids with new skeletons, together with their biosynthetic precursors (), were isolated from the flowers of Gelsemium elegans. Compounds and represent the first examples of trimeric Gelsemium alkaloids that feature complex sterically compact frameworks with 17–19 chiral centers. Furthermore, these compounds were constructed through unprecedented C14–C19 and C14–N4 linkages. Interestingly, all these oligomeric alkaloids () could be derived from the same monomer precursor in the proposed biogenetic pathway. The anti-inflammatory and anti-fibrotic activities of these isolates were evaluated, and compound demonstrated potent effects in vitro and in vivo. The biomimetic synthesis of was achieved according to the proposed biogenetic pathway.
{"title":"Oligomeric monoterpenoid indole alkaloids from the flowers of Gelsemium elegans with anti-inflammatory and anti-fibrotic activities†","authors":"Ji-Hong Gu , Ni-Ping Li , Hao-Ting Lin , Ling-Na Dai , Min-Jing Cheng , Jian Hong , Yi-Yi Li , Jun-Shan Liu , Wen-Cai Ye , Lei Wang","doi":"10.1039/d5qo00551e","DOIUrl":"10.1039/d5qo00551e","url":null,"abstract":"<div><div>Gelsepolycines A–F (), six oligomeric monoterpenoid indole alkaloids with new skeletons, together with their biosynthetic precursors (), were isolated from the flowers of <em>Gelsemium elegans</em>. Compounds and represent the first examples of trimeric <em>Gelsemium</em> alkaloids that feature complex sterically compact frameworks with 17–19 chiral centers. Furthermore, these compounds were constructed through unprecedented C<sub>14</sub>–C<sub>19</sub> and C<sub>14</sub>–N<sub>4</sub> linkages. Interestingly, all these oligomeric alkaloids () could be derived from the same monomer precursor in the proposed biogenetic pathway. The anti-inflammatory and anti-fibrotic activities of these isolates were evaluated, and compound demonstrated potent effects <em>in vitro</em> and <em>in vivo</em>. The biomimetic synthesis of was achieved according to the proposed biogenetic pathway.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5387-5394"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201545","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}
A sub-stoichiometric sodium hydride promoted strategy with diselenides and disulphides has been devised for the one-pot cascade oxidation/aromatization and regioselective C-3 selenylation/sulfenylation of indolines under transition metal-free conditions. The newly introduced protocol facilitates the synthesis of C-3 chalcogenated indoles with exceptional flexibility and efficiency. The chalcogenation reaction was successfully performed under both aerobic and inert conditions leading to the formation of C-3 chalcogenated indoles via two different intermediates. Mechanistic insights were derived from various controlled experiments and trapping of reaction intermediates under both sets of conditions, with structural verification achieved via spectral analysis. The prevalence of the radical route was validated by EPR spectroscopy and radical quenching experiments. A broad range of 3-arylthioindoles and 3-arylselenylindoles containing electron donating and withdrawing substituents were obtained in high to excellent yields with this modest and environmentally benign protocol. Additionally, post-transformation of sulfenylated derivatives has further led to the generation of a diarylsulfoxide core of pharmaceutical interest. The reaction is applicable to gram scale synthesis without significant loss of product yield, indicating its application for large-scale synthesis. Interestingly, the biological evaluation of the 5-bromo-3-((4-(trifluoromethyl)phenyl)selanyl)-1H-indole and 3-((4-chlorophenyl)thio)-1H-indole revealed significant activity against rapidly growing mycobacteria (RGM).
{"title":"NaH-promoted one-pot oxidation/aromatization and C-3H chalcogenation of indoline: atmospheric control-based selective intermediates†","authors":"Suman Majee , Km. Anjali , Shaily Agarwal , Vishnu Poonia , Alok Kumar Singh , Biswajit Guchhait , Devalina Ray","doi":"10.1039/d5qo00576k","DOIUrl":"10.1039/d5qo00576k","url":null,"abstract":"<div><div>A sub-stoichiometric sodium hydride promoted strategy with diselenides and disulphides has been devised for the one-pot cascade oxidation/aromatization and regioselective C-3 selenylation/sulfenylation of indolines under transition metal-free conditions. The newly introduced protocol facilitates the synthesis of C-3 chalcogenated indoles with exceptional flexibility and efficiency. The chalcogenation reaction was successfully performed under both aerobic and inert conditions leading to the formation of C-3 chalcogenated indoles <em>via</em> two different intermediates. Mechanistic insights were derived from various controlled experiments and trapping of reaction intermediates under both sets of conditions, with structural verification achieved <em>via</em> spectral analysis. The prevalence of the radical route was validated by EPR spectroscopy and radical quenching experiments. A broad range of 3-arylthioindoles and 3-arylselenylindoles containing electron donating and withdrawing substituents were obtained in high to excellent yields with this modest and environmentally benign protocol. Additionally, post-transformation of sulfenylated derivatives has further led to the generation of a diarylsulfoxide core of pharmaceutical interest. The reaction is applicable to gram scale synthesis without significant loss of product yield, indicating its application for large-scale synthesis. Interestingly, the biological evaluation of the 5-bromo-3-((4-(trifluoromethyl)phenyl)selanyl)-1<em>H</em>-indole and 3-((4-chlorophenyl)thio)-1<em>H</em>-indole revealed significant activity against rapidly growing mycobacteria (RGM).</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5496-5503"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144184090","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}
Pub Date : 2025-09-05Epub Date: 2025-06-23DOI: 10.1039/d5qo00618j
Kemeng Zhang , Shuodan Ding , Jie Zhou , Xinyu Zhou , Ge Wu , XinLei Wu
Bunte salts are frequently utilized as effective thiolation reagents for constructing thioethers. In this study, we discovered that Bunte salts could also serve as mediators to enable the oxidative C–H sulfonation of alkenes with sodium sulfinates. Mechanistically, alkyl sulfides are generated as key intermediates, which undergo an unusual oxidative elimination to give the corresponding products. These tandem addition–elimination reactions allow for the conversion of various styrenes and α-alkyl styrenes into vinyl and allylic sulfones in useful to excellent yields.
{"title":"Bunte salt-mediated sulfonation of alkenes with sodium sulfinates†","authors":"Kemeng Zhang , Shuodan Ding , Jie Zhou , Xinyu Zhou , Ge Wu , XinLei Wu","doi":"10.1039/d5qo00618j","DOIUrl":"10.1039/d5qo00618j","url":null,"abstract":"<div><div>Bunte salts are frequently utilized as effective thiolation reagents for constructing thioethers. In this study, we discovered that Bunte salts could also serve as mediators to enable the oxidative C–H sulfonation of alkenes with sodium sulfinates. Mechanistically, alkyl sulfides are generated as key intermediates, which undergo an unusual oxidative elimination to give the corresponding products. These tandem addition–elimination reactions allow for the conversion of various styrenes and α-alkyl styrenes into vinyl and allylic sulfones in useful to excellent yields.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5616-5621"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341381","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}
Pub Date : 2025-09-05Epub Date: 2025-06-11DOI: 10.1039/d5qo00725a
Ryu Tadano , Takeshi Yasui , Yoshihiko Yamamoto
Kinetic resolution of benzhydrols via intramolecular C–H silylation is an efficient method for the preparation of chiral benzhydrols. However, the previously reported methods required sterically demanding phenyl rings to achieve group-selective C–H silylation. Herein, we report the kinetic resolution of trifluoromethylated heterobenzhydrols, bearing both phenyl and thiophene rings, via heteroaryl-selective C–H silylation. We conducted computational studies on the factors influencing the enantioselectivity and heteroaryl selectivity.
{"title":"Kinetic resolution of trifluoromethylated heterobenzhydrols via hydrogen-acceptor-free Ir-catalyzed heteroaryl-selective C–H silylation†","authors":"Ryu Tadano , Takeshi Yasui , Yoshihiko Yamamoto","doi":"10.1039/d5qo00725a","DOIUrl":"10.1039/d5qo00725a","url":null,"abstract":"<div><div>Kinetic resolution of benzhydrols <em>via</em> intramolecular C–H silylation is an efficient method for the preparation of chiral benzhydrols. However, the previously reported methods required sterically demanding phenyl rings to achieve group-selective C–H silylation. Herein, we report the kinetic resolution of trifluoromethylated heterobenzhydrols, bearing both phenyl and thiophene rings, <em>via</em> heteroaryl-selective C–H silylation. We conducted computational studies on the factors influencing the enantioselectivity and heteroaryl selectivity.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5525-5532"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144268909","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}
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