Pub Date : 2026-02-09DOI: 10.1021/acs.orglett.6c00002
Zi-Ru Xu,Hui Gao,Pei-Long Wang,Hongyu Wang
The first example of the electrochemical C(sp3)–H amination of inactive hydrocarbons with sulfoximines was reported. We proposed the concept of an NH3-induced electrochemical reaction for the first time. Although the electrochemical C(sp3)–H functionalization of inactive linear hydrocarbons is difficult (especially for alkynes), this reaction is suitable for both linear and cyclic hydrocarbons; the reaction is advantageous because it is green, generates minimal waste (with H2 as the only byproduct), proceeds without transition metal and external oxidant, and requires mild reaction conditions.
{"title":"A General Electrochemical C(sp3)–H Amination of Hydrocarbons Suitable for Inactive Alkanes, Alkenes and Alkynes","authors":"Zi-Ru Xu,Hui Gao,Pei-Long Wang,Hongyu Wang","doi":"10.1021/acs.orglett.6c00002","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00002","url":null,"abstract":"The first example of the electrochemical C(sp3)–H amination of inactive hydrocarbons with sulfoximines was reported. We proposed the concept of an NH3-induced electrochemical reaction for the first time. Although the electrochemical C(sp3)–H functionalization of inactive linear hydrocarbons is difficult (especially for alkynes), this reaction is suitable for both linear and cyclic hydrocarbons; the reaction is advantageous because it is green, generates minimal waste (with H2 as the only byproduct), proceeds without transition metal and external oxidant, and requires mild reaction conditions.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"9 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.orglett.5c05166
Hemonta Kumar Saha,Tarun,Vishvajeet Kumar,Dibyendu Mallick,Upendra Kumar Pandey,Soumyajit Das
N-Annulated [5]helicene (NH5) and its dibenzo-extended derivatives are synthesized by cycloisomerization and Scholl-type cyclodehydrogenation methods, respectively. Nitrogen-bridging of fjord-carbons 1 and 14 of [5]helicene endows saddle-like NH5 featuring an antiaromatic azepine core with enhanced orbital overlap between nitrogen and the carbon π-system. N-Annulation results in less stabilized HOMO, a smaller HOMO–LUMO energy gap, red-shifted absorption, fluorescence, paratropic ring current over the azepine unit, and tunable aromaticity of the core relative to pristine [5]helicene. The NH5 derivatives exhibit space-charge-limited current hole mobility on the order of 10–3 cm2 V–1 s–1, which is higher than that of N-annulated PAH, like N-annulated perylene.
{"title":"N-Annulated [5]Helicenes: Syntheses, (Anti)Aromaticity and Properties","authors":"Hemonta Kumar Saha,Tarun,Vishvajeet Kumar,Dibyendu Mallick,Upendra Kumar Pandey,Soumyajit Das","doi":"10.1021/acs.orglett.5c05166","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05166","url":null,"abstract":"N-Annulated [5]helicene (NH5) and its dibenzo-extended derivatives are synthesized by cycloisomerization and Scholl-type cyclodehydrogenation methods, respectively. Nitrogen-bridging of fjord-carbons 1 and 14 of [5]helicene endows saddle-like NH5 featuring an antiaromatic azepine core with enhanced orbital overlap between nitrogen and the carbon π-system. N-Annulation results in less stabilized HOMO, a smaller HOMO–LUMO energy gap, red-shifted absorption, fluorescence, paratropic ring current over the azepine unit, and tunable aromaticity of the core relative to pristine [5]helicene. The NH5 derivatives exhibit space-charge-limited current hole mobility on the order of 10–3 cm2 V–1 s–1, which is higher than that of N-annulated PAH, like N-annulated perylene.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"284 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.orglett.6c00165
Changyin Zhao,Yuzhen Dong,Hongbin Liu,Jiazheng Wu,Minghui Zhu,Lei Liu,Xigong Liu
A biomimetic iron-catalyzed system has been developed for the selective oxidation of 3-substituted indoles to 3-monosubstituted 2-oxindoles using H2O2 as a green oxidant under mild conditions. This catalytic approach addresses the drawbacks of stoichiometric biomimetic models and exhibits broad substrate scope and excellent functional group tolerance. Mechanistic studies suggest the reaction proceeds via an epoxide intermediate followed by a 2,3-hydride shift, with the epoxidation step being rate-determining. The method provides a sustainable route to biologically relevant 2-oxindole scaffolds.
{"title":"Biomimetic Iron-Catalyzed Oxidation of 3-Substituted Indoles to 2-Oxindoles","authors":"Changyin Zhao,Yuzhen Dong,Hongbin Liu,Jiazheng Wu,Minghui Zhu,Lei Liu,Xigong Liu","doi":"10.1021/acs.orglett.6c00165","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00165","url":null,"abstract":"A biomimetic iron-catalyzed system has been developed for the selective oxidation of 3-substituted indoles to 3-monosubstituted 2-oxindoles using H2O2 as a green oxidant under mild conditions. This catalytic approach addresses the drawbacks of stoichiometric biomimetic models and exhibits broad substrate scope and excellent functional group tolerance. Mechanistic studies suggest the reaction proceeds via an epoxide intermediate followed by a 2,3-hydride shift, with the epoxidation step being rate-determining. The method provides a sustainable route to biologically relevant 2-oxindole scaffolds.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"24 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We report a visible-light-induced strategy for synthesizing lactone-fused indolines via the radical dearomatization of indoles with simple alcohols. This method combines hydrogen atom transfer (HAT) catalysis and Lewis acid activation operating under ambient conditions. The protocol exhibits a broad substrate scope and excellent diastereoselectivity, leveraging readily available alcohols as alkyl radical precursors. This sustainable approach provides efficient access to complex heterocyclic scaffolds commonly found in bioactive natural products.
{"title":"Visible-Light-Induced Lactone-Fused Indoline Construction via Radical Dearomatization of Indoles with Alcohols","authors":"Jingshan Ai,Qihang Xu,Yaru Liu,Yongcan Liu,Yuchen Teng,Wengang Xu,Qiao Zhang,Mingbo Wu","doi":"10.1021/acs.orglett.6c00303","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00303","url":null,"abstract":"We report a visible-light-induced strategy for synthesizing lactone-fused indolines via the radical dearomatization of indoles with simple alcohols. This method combines hydrogen atom transfer (HAT) catalysis and Lewis acid activation operating under ambient conditions. The protocol exhibits a broad substrate scope and excellent diastereoselectivity, leveraging readily available alcohols as alkyl radical precursors. This sustainable approach provides efficient access to complex heterocyclic scaffolds commonly found in bioactive natural products.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"51 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.orglett.6c00078
Casey J. McCarthy,Marius Müller,Richard Ma,Umberto Maria Battisti,Jay S. Wright,E. William Webb,Melanie S. Sanford,Matthias M. Herth,Peter J. H. Scott
Radiocyanation is an attractive approach to introduce carbon-11 into radiopharmaceuticals, as nitriles and other acyl moieties. This report describes a Friedel–Crafts-type electrophilic radiocyanation of (hetero)aryltrimethylgermanes and trimethylstannanes as well as a direct C–H radiocyanation of (hetero)arenes. This approach leverages the in situ oxidation of [11C]CN– to [11C]CNCl to enable electrophilic aromatic substitution pathways for accessing relevant 11C-aryl nitrile scaffolds. This method proceeds in short reaction times with readily available, shelf-stable reagents and enables radiocyanation of diverse substrates in good radiochemical yields.
{"title":"Friedel–Crafts-Type Electrophilic Radiocyanation of (Hetero)arenes","authors":"Casey J. McCarthy,Marius Müller,Richard Ma,Umberto Maria Battisti,Jay S. Wright,E. William Webb,Melanie S. Sanford,Matthias M. Herth,Peter J. H. Scott","doi":"10.1021/acs.orglett.6c00078","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00078","url":null,"abstract":"Radiocyanation is an attractive approach to introduce carbon-11 into radiopharmaceuticals, as nitriles and other acyl moieties. This report describes a Friedel–Crafts-type electrophilic radiocyanation of (hetero)aryltrimethylgermanes and trimethylstannanes as well as a direct C–H radiocyanation of (hetero)arenes. This approach leverages the in situ oxidation of [11C]CN– to [11C]CNCl to enable electrophilic aromatic substitution pathways for accessing relevant 11C-aryl nitrile scaffolds. This method proceeds in short reaction times with readily available, shelf-stable reagents and enables radiocyanation of diverse substrates in good radiochemical yields.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"43 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.orglett.6c00064
Xingchun Sun,Xiao-Lin Zhang,Xin-Ru Qiao,Han Ding,Kan Zhong,Ming Li,Xue-Wei Liu
Thioglycoside preactivation enables one-pot oligosaccharide assembly but relies on unstable sulfenyl chloride activators. We report a user-friendly manifold that forms sulfenyl chlorides in seconds from common thiols and N-chlorosuccinimide, with succinimide precipitating and the clear supernatant serving as a drop-in activator solution. The protocol tolerates the substrate scope, accommodating special stereoselective glycosylation reactions and iterative one-pot sequences. A concise synthesis of a human milk tetrasaccharide demonstrates rapid one-pot access to a biologically relevant motif.
{"title":"User-Friendly Thioglycoside Preactivation via Instant Sulfenyl Chloride Generation","authors":"Xingchun Sun,Xiao-Lin Zhang,Xin-Ru Qiao,Han Ding,Kan Zhong,Ming Li,Xue-Wei Liu","doi":"10.1021/acs.orglett.6c00064","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00064","url":null,"abstract":"Thioglycoside preactivation enables one-pot oligosaccharide assembly but relies on unstable sulfenyl chloride activators. We report a user-friendly manifold that forms sulfenyl chlorides in seconds from common thiols and N-chlorosuccinimide, with succinimide precipitating and the clear supernatant serving as a drop-in activator solution. The protocol tolerates the substrate scope, accommodating special stereoselective glycosylation reactions and iterative one-pot sequences. A concise synthesis of a human milk tetrasaccharide demonstrates rapid one-pot access to a biologically relevant motif.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"241 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.orglett.6c00354
Jie Gong,Fang Wang,Shu-hui Lei,Yan-Biao Kang,Jian-Ping Qu
Herein, we report a photocatalytic synthesis of α-fluoro-β-sulfonyl carbonyl compounds using nucleophilic fluorine sources under photo redox-neutral conditions. The key to this transformation is the generation of α-carbonyl carbocations via single-electron oxidation of β-sulfonyl-α-carbonyl radicals, which are formed through regioselective sulfonyl radical addition to α,β-unsaturated carbonyl compounds. This method offers efficient and general access to structurally diverse α-fluorinated carbonyl building blocks, expanding the synthetic toolbox for fluorinated molecule construction.
{"title":"Photocatalytic Synthesis of α-Fluoro-β-sulfonyl Carbonyl Compounds Using Nucleophilic Fluorine Sources","authors":"Jie Gong,Fang Wang,Shu-hui Lei,Yan-Biao Kang,Jian-Ping Qu","doi":"10.1021/acs.orglett.6c00354","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00354","url":null,"abstract":"Herein, we report a photocatalytic synthesis of α-fluoro-β-sulfonyl carbonyl compounds using nucleophilic fluorine sources under photo redox-neutral conditions. The key to this transformation is the generation of α-carbonyl carbocations via single-electron oxidation of β-sulfonyl-α-carbonyl radicals, which are formed through regioselective sulfonyl radical addition to α,β-unsaturated carbonyl compounds. This method offers efficient and general access to structurally diverse α-fluorinated carbonyl building blocks, expanding the synthetic toolbox for fluorinated molecule construction.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"284 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.orglett.6c00049
Inho Jang,Hun Young Kim,Kyungsoo Oh
The development of general anti-Markovnikov hydroalkoxylation methods remains challenging due to competing alkene oxidation and photocatalyst–alcohol compatibility issues. Herein, diaryl diselenides serve as efficient electron-shuttle catalysts for visible-light-driven anti-Markovnikov hydroalkoxylation in combination with TPT+BF4–. A broad range of aryl- and alkyl-substituted alkenes and diverse alcohols are accommodated, affording products up to 97% yield. Mechanistic studies reveal a diselenide-mediated, multistep electron-shuttle pathway that enables mild and selective transformations.
{"title":"Electron-Shuttle Catalysis by Diaryl Diselenides for Photochemical Anti-Markovnikov Hydroalkoxylation of Alkenes","authors":"Inho Jang,Hun Young Kim,Kyungsoo Oh","doi":"10.1021/acs.orglett.6c00049","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00049","url":null,"abstract":"The development of general anti-Markovnikov hydroalkoxylation methods remains challenging due to competing alkene oxidation and photocatalyst–alcohol compatibility issues. Herein, diaryl diselenides serve as efficient electron-shuttle catalysts for visible-light-driven anti-Markovnikov hydroalkoxylation in combination with TPT+BF4–. A broad range of aryl- and alkyl-substituted alkenes and diverse alcohols are accommodated, affording products up to 97% yield. Mechanistic studies reveal a diselenide-mediated, multistep electron-shuttle pathway that enables mild and selective transformations.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"217 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139054","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.orglett.5c05332
Min Shen,Nian-Hua Luo,Guo-Dong Zhu,Zhi-Yang Zhou,Cheng Fu,Xin-Yun Zhong,He-Bin Huang,Xiang-Jun Peng
A Ce-base-controlled and visible-light-induced approach enables the cleavage of NTf-pyridiniums into various 2-polyene sulfonylpyridines. This Zincke-like reaction involves the conversion of pyridines into electron-rich intermediates and subsequent regioselective electrophilic modification through the formation of an EDA complex, intermolecular single-electron transfer, radical coupling, and selective C2–N bond cleavage. In addition, the obtained 2-polyene sulfonylpyridine 2a displays interesting photophysical properties.
{"title":"Photochemical Zincke-like Reactions Enabled the Expeditious Synthesis of 2-Polyene Sulfonylpyridines","authors":"Min Shen,Nian-Hua Luo,Guo-Dong Zhu,Zhi-Yang Zhou,Cheng Fu,Xin-Yun Zhong,He-Bin Huang,Xiang-Jun Peng","doi":"10.1021/acs.orglett.5c05332","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05332","url":null,"abstract":"A Ce-base-controlled and visible-light-induced approach enables the cleavage of NTf-pyridiniums into various 2-polyene sulfonylpyridines. This Zincke-like reaction involves the conversion of pyridines into electron-rich intermediates and subsequent regioselective electrophilic modification through the formation of an EDA complex, intermolecular single-electron transfer, radical coupling, and selective C2–N bond cleavage. In addition, the obtained 2-polyene sulfonylpyridine 2a displays interesting photophysical properties.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"108 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, dual photoredox/CpTi(IV) catalysis has been developed for the reductive cyclization of 3a-bromo-hexahydropyrroloindoline or 3-bromo-tetrahydrofuroindole with the appendage nitrile, providing rapid access to a series of 4a,9a-heterocycle-fused tetrahydrocarbazoles in satisfactory yields. Utilizing this methodology, formal synthesis of minfiensine, strictamine, and aspidophylline A was achieved based on a sequential catalytic asymmetric bromocyclization/reductive cyclization with improved synthetic efficiency for demonstrating its broad synthetic potential.
{"title":"Dual Photoredox/CpTi(IV)-Catalyzed Reductive Cyclization of Tertiary Bromide with Nitrile for Constructing 4a,9a-Heterocycle-Fused Tetrahydrocarbazole","authors":"Yanxia Zhen,Zhijiang Ma,Guanghui Fan,Xiaoran Shi,Junhan Chen,Jiyou Huo,Jiahang Yan,Weiqing Xie","doi":"10.1021/acs.orglett.5c05091","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05091","url":null,"abstract":"In this study, dual photoredox/CpTi(IV) catalysis has been developed for the reductive cyclization of 3a-bromo-hexahydropyrroloindoline or 3-bromo-tetrahydrofuroindole with the appendage nitrile, providing rapid access to a series of 4a,9a-heterocycle-fused tetrahydrocarbazoles in satisfactory yields. Utilizing this methodology, formal synthesis of minfiensine, strictamine, and aspidophylline A was achieved based on a sequential catalytic asymmetric bromocyclization/reductive cyclization with improved synthetic efficiency for demonstrating its broad synthetic potential.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"1 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139062","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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