Pub Date : 2026-02-04DOI: 10.1021/acs.orglett.5c05428
Lu Gan,Xin-Yi Hu,Rong Huang,Li-Fen Ma,Dean Guo,Wei Li
Two heterodimeric sesquiterpenoids, chlorjaponoids A (1) and B (2), were isolated from the whole plants of Chloranthus japonicus. Their structures, characterized by a unique cage-like tetracyclo[8.5.0.02,7.03,13]pentadecane scaffold, were elucidated by comprehensive spectroscopic analysis and confirmed by single-crystal X-ray diffraction. Both compounds demonstrated antihepatic fibrosis activity in vitro.
{"title":"Chlorjaponoids A and B, Two Lindenane–Guaiane Sesquiterpenoid Dimers with a Cage-like Tetracyclo[8.5.0.02,7.03,13]pentadecane Scaffold from Chloranthus japonicus","authors":"Lu Gan,Xin-Yi Hu,Rong Huang,Li-Fen Ma,Dean Guo,Wei Li","doi":"10.1021/acs.orglett.5c05428","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05428","url":null,"abstract":"Two heterodimeric sesquiterpenoids, chlorjaponoids A (1) and B (2), were isolated from the whole plants of Chloranthus japonicus. Their structures, characterized by a unique cage-like tetracyclo[8.5.0.02,7.03,13]pentadecane scaffold, were elucidated by comprehensive spectroscopic analysis and confirmed by single-crystal X-ray diffraction. Both compounds demonstrated antihepatic fibrosis activity in vitro.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"8 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111165","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 : 2026-02-04DOI: 10.1021/acs.orglett.5c05452
Sunday Adewale Akintelu,Sikabwe Noki,Kwazi Masuku,Hossain Saneii,Beatriz G. de la Torre,Fernando Albericio
A safety-catch protecting group allows for the use of the same reagent/chemical mechanism for the removal of different protecting groups in the same synthetic scheme. While the first of these is removed directly, the removal of the second requires previous manipulation to make the protecting group labile to the reagent. Herein, phenylthioethyl (Pte)- and phenylsulfonylethyl (Pse)-based protecting groups are described. While Pte is stable to piperidine, Pse, which is its oxidized form, is labile in the presence of DBU-methylpiperidine. This system allows the preparation of linear, branched, cyclic, and other complex peptides.
{"title":"Phenylthioethyl (Pte)/Phenylsulfonylethyl (Pse) as Safety Catch Protecting Groups for Peptide Synthesis","authors":"Sunday Adewale Akintelu,Sikabwe Noki,Kwazi Masuku,Hossain Saneii,Beatriz G. de la Torre,Fernando Albericio","doi":"10.1021/acs.orglett.5c05452","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05452","url":null,"abstract":"A safety-catch protecting group allows for the use of the same reagent/chemical mechanism for the removal of different protecting groups in the same synthetic scheme. While the first of these is removed directly, the removal of the second requires previous manipulation to make the protecting group labile to the reagent. Herein, phenylthioethyl (Pte)- and phenylsulfonylethyl (Pse)-based protecting groups are described. While Pte is stable to piperidine, Pse, which is its oxidized form, is labile in the presence of DBU-methylpiperidine. This system allows the preparation of linear, branched, cyclic, and other complex peptides.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"91 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111166","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 : 2026-02-04DOI: 10.1021/acs.orglett.6c00102
Azusa Kondoh,Masahiro Terada
A Brønsted base-catalyzed aminoxylation of benzylic and allylic compounds was developed. The reaction differs mechanistically from the existing aminoxylation of simple hydrocarbons and involves the catalytic generation of benzyl and allyl radicals via single electron transfer between carbanions and TEMPO. Its synthetic benefits were demonstrated by employing it in various catalytic tandem reaction systems.
{"title":"Brønsted Base-Catalyzed Aminoxylation of Benzylic and Allylic Compounds with TEMPO","authors":"Azusa Kondoh,Masahiro Terada","doi":"10.1021/acs.orglett.6c00102","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00102","url":null,"abstract":"A Brønsted base-catalyzed aminoxylation of benzylic and allylic compounds was developed. The reaction differs mechanistically from the existing aminoxylation of simple hydrocarbons and involves the catalytic generation of benzyl and allyl radicals via single electron transfer between carbanions and TEMPO. Its synthetic benefits were demonstrated by employing it in various catalytic tandem reaction systems.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"41 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111170","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 : 2026-02-04DOI: 10.1021/acs.orglett.5c05322
Mei Bai,Chaoqun Shi,Minghui Sun,Cheng Ma,Shasha Geng,Wei Xiang,Jinping Yuan,Shao-Fei Ni,Zhang Feng
We present a NaHMDS-promoted method for the efficient and highly selective synthesis of aryl boronates from carbonyl compounds. This approach offers several advantages, including environmental sustainability, the absence of halogenated waste, and no need for catalysts and additives. These protocols enable the late-stage borylation of biorelevant compounds, thus offering a versatile platform for synthesizing diverse naphthalene derivatives from carbonyls. Experimental studies suggest that the reaction involves alkenyl C–O bond borylation and desaturation processes. Notably, the NaHMDS/diboron reagent system demonstrates unprecedented oxidative properties rather than its more commonly encountered reductive properties, which will open new avenues for designing transformations using this platform.
{"title":"Merging Borylation and Desaturation to Access Arylboronates from Carbonyls","authors":"Mei Bai,Chaoqun Shi,Minghui Sun,Cheng Ma,Shasha Geng,Wei Xiang,Jinping Yuan,Shao-Fei Ni,Zhang Feng","doi":"10.1021/acs.orglett.5c05322","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05322","url":null,"abstract":"We present a NaHMDS-promoted method for the efficient and highly selective synthesis of aryl boronates from carbonyl compounds. This approach offers several advantages, including environmental sustainability, the absence of halogenated waste, and no need for catalysts and additives. These protocols enable the late-stage borylation of biorelevant compounds, thus offering a versatile platform for synthesizing diverse naphthalene derivatives from carbonyls. Experimental studies suggest that the reaction involves alkenyl C–O bond borylation and desaturation processes. Notably, the NaHMDS/diboron reagent system demonstrates unprecedented oxidative properties rather than its more commonly encountered reductive properties, which will open new avenues for designing transformations using this platform.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"280 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111255","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 : 2026-02-04DOI: 10.1021/acs.orglett.6c00089
Yi-Lin Zhao,Xiao-Ling Jin,Qiang Liu
N-Nitrosamines serve as bifunctional reagents to install both amino and nitroso groups across unsaturated bonds, yet their use as diamine reagents remains underdeveloped. Herein, we introduce a simple yellow-light-driven reaction that directly forms amidoximes from N-nitrososulfonamides and diazo compounds. The process works by selectively activating the N–NO bond with low-energy light (λ > 590 nm), thereby avoiding side reactions and ensuring high selectivity.
n -亚硝胺作为双功能试剂在不饱和键上安装氨基和亚硝基，但它们作为二胺试剂的应用尚不发达。在这里，我们介绍了一个简单的黄光驱动反应，直接从n -亚硝基磺胺和重氮化合物生成偕胺肟。该工艺通过低能光（λ > 590 nm）选择性激活N-NO键，从而避免副反应并确保高选择性。
{"title":"Yellow-Light-Mediated Synthesis of Amidoximes via Radical gem-Diamination of Diazo Compounds","authors":"Yi-Lin Zhao,Xiao-Ling Jin,Qiang Liu","doi":"10.1021/acs.orglett.6c00089","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00089","url":null,"abstract":"N-Nitrosamines serve as bifunctional reagents to install both amino and nitroso groups across unsaturated bonds, yet their use as diamine reagents remains underdeveloped. Herein, we introduce a simple yellow-light-driven reaction that directly forms amidoximes from N-nitrososulfonamides and diazo compounds. The process works by selectively activating the N–NO bond with low-energy light (λ > 590 nm), thereby avoiding side reactions and ensuring high selectivity.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"1 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111164","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 : 2026-02-04DOI: 10.1021/acs.orglett.5c05422
Zhang-Long Yu,Yan Tan,Jin-Xiong Chen,Zi-Jun Liu,Xiang Liang,He-Sheng Xiao,Qiang Wang,Xiao-Ji Wang
A general copper-catalyzed intermolecular aminotrifluoromethylation of alkenes with free anilines and Togni’s reagent is reported. Distinguished by its versatile reactivity, this protocol enables the coupling of diverse primary and secondary anilines ranging from electron-deficient to oxidatively sensitive electron-rich substrates. The reaction features mild conditions and accommodates a wide range of alkenes, including styrenes, α-substituted styrenes, and unactivated alkenes. This method provides a robust platform for accessing β-trifluoromethyl amines, including those with quaternary carbon centers, and is applicable to the late-stage functionalization of pharmaceutical derivatives.
{"title":"Copper-Catalyzed Intermolecular Aminotrifluoromethylation of Alkenes with Free Anilines","authors":"Zhang-Long Yu,Yan Tan,Jin-Xiong Chen,Zi-Jun Liu,Xiang Liang,He-Sheng Xiao,Qiang Wang,Xiao-Ji Wang","doi":"10.1021/acs.orglett.5c05422","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05422","url":null,"abstract":"A general copper-catalyzed intermolecular aminotrifluoromethylation of alkenes with free anilines and Togni’s reagent is reported. Distinguished by its versatile reactivity, this protocol enables the coupling of diverse primary and secondary anilines ranging from electron-deficient to oxidatively sensitive electron-rich substrates. The reaction features mild conditions and accommodates a wide range of alkenes, including styrenes, α-substituted styrenes, and unactivated alkenes. This method provides a robust platform for accessing β-trifluoromethyl amines, including those with quaternary carbon centers, and is applicable to the late-stage functionalization of pharmaceutical derivatives.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"88 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111167","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 : 2026-02-04DOI: 10.1021/acs.orglett.5c05099
Rongxin Yang,Fuqiao Xing,Hongjian Song,Yuxiu Liu,Qingmin Wang
We have developed a green electrochemical method for azidoarylthiation of styrenes and enol ethers by employing trimethylsilyl azide as a nucleophile and diaryl disulfides and aryl thiols as atom-economical arylthio sources under oxidant- and metal-free conditions. β-Azido aryl sulfides were obtained in moderate to good yields, and the reaction showed good functional group tolerance. This method avoids the formation of 1,2-disulfides and 1,2-diazides and controls the regioselectivity of the reactions while providing a good starting point for the synthesis of functionalized β-amino aryl sulfides and triazolo aryl sulfides.
{"title":"Electrochemical Azidoarylthiation of Aryl Olefin and Enol Ethers","authors":"Rongxin Yang,Fuqiao Xing,Hongjian Song,Yuxiu Liu,Qingmin Wang","doi":"10.1021/acs.orglett.5c05099","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05099","url":null,"abstract":"We have developed a green electrochemical method for azidoarylthiation of styrenes and enol ethers by employing trimethylsilyl azide as a nucleophile and diaryl disulfides and aryl thiols as atom-economical arylthio sources under oxidant- and metal-free conditions. β-Azido aryl sulfides were obtained in moderate to good yields, and the reaction showed good functional group tolerance. This method avoids the formation of 1,2-disulfides and 1,2-diazides and controls the regioselectivity of the reactions while providing a good starting point for the synthesis of functionalized β-amino aryl sulfides and triazolo aryl sulfides.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"20 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111169","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}
The carbocation is one of the highly reactive intermediates in synthetic chemistry; however, catalytic selective transformations involving vinylic cation species remain elusive in comparison to sp2-hybrid ones. Herein, we report a Rh-catalyzed formal C–H and X–H insertion reaction of in situ-generated exocyclic vinylic cations with a variety of nucleophiles, affording tetrasubstituted alkenes incorporating a cyclobutanone motif with a broad substrate scope under mild conditions. The utility of this method has been demonstrated for the synthesis of 3-methylenecyclobutanone derivatives, which are difficult to access using other methods, serving as versatile building blocks for a range of postfunctionalization conversions.
{"title":"Rhodium-Catalyzed Formal C–H and X–H Insertion Reaction Involving an Exocyclic Vinylic Cation Intermediate","authors":"Kemiao Hong,Shasha Chen,Jingxian Li,Zhuofeng Ke,Xinfang Xu","doi":"10.1021/acs.orglett.5c05314","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05314","url":null,"abstract":"The carbocation is one of the highly reactive intermediates in synthetic chemistry; however, catalytic selective transformations involving vinylic cation species remain elusive in comparison to sp2-hybrid ones. Herein, we report a Rh-catalyzed formal C–H and X–H insertion reaction of in situ-generated exocyclic vinylic cations with a variety of nucleophiles, affording tetrasubstituted alkenes incorporating a cyclobutanone motif with a broad substrate scope under mild conditions. The utility of this method has been demonstrated for the synthesis of 3-methylenecyclobutanone derivatives, which are difficult to access using other methods, serving as versatile building blocks for a range of postfunctionalization conversions.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"1 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111168","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}
Under acidic conditions, propargylic alcohols undergo Meyer–Schuster or Rupe rearrangements to afford two isomeric α,β-unsaturated ketones. Herein, we disclose a mechanistically distinct base-mediated regioselective conversion of TMS ethers of propargylic alcohols to 1,3-enynes in high yields with broad functional-group compatibility. Alternatively, trapping of the in situ-generated lithium acetylide with electrophiles enables access to functionalized internal 1,3-enynes. Owing to the ready accessibility of propargylic alcohols, this method provides a practical and attractive entry to synthetically valuable 1,3-enynes.
{"title":"Base-Promoted Conversion of Propargylic Alcohols to 1,3-Enynes","authors":"Morgane Delattre,Milena Wiegand,Qian Wang,Jieping Zhu","doi":"10.1021/acs.orglett.6c00196","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00196","url":null,"abstract":"Under acidic conditions, propargylic alcohols undergo Meyer–Schuster or Rupe rearrangements to afford two isomeric α,β-unsaturated ketones. Herein, we disclose a mechanistically distinct base-mediated regioselective conversion of TMS ethers of propargylic alcohols to 1,3-enynes in high yields with broad functional-group compatibility. Alternatively, trapping of the in situ-generated lithium acetylide with electrophiles enables access to functionalized internal 1,3-enynes. Owing to the ready accessibility of propargylic alcohols, this method provides a practical and attractive entry to synthetically valuable 1,3-enynes.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"1 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111172","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}
Despite the broad utility of cyclic diaryl λ3-bromanes as aryne precursors for nucleophilic additions by heteroatom-based nucleophiles under mild basic conditions, their capacity to install arylchalcogen bonds in a regioselective manner is largely unexplored and challenging. The higher oxidative addition barrier of cyclic diaryl λ3-bromanes relative to their iodine analogues leads to transition-metal-catalyzed aryl–chalcogen bond formation requiring more forcing conditions, which decreases the regioselectivity. Moreover, the oxidizing character of hypervalent bromanes might be problematic. Herein, we disclose a photocatalytic strategy to achieve highly regioselective thiolation and selenylation of cyclic diaryl λ3-bromanes. This reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with a good functional group tolerance and excellent regioselectivity.
{"title":"Regioselective Thiolation and Selenylation of Cyclic Diaryl λ3-Bromanes Enabled by Visible-Light Photocatalysis","authors":"Xue-Ying Yang,Qiang Wang,Si-Rui Jia,Shi-Yu Fu,Ming-Chuan Wang,Zhi-Yue Dong,Wan-Xuan Zhang,Bin-Jie Li,Wen-Jing Xiao","doi":"10.1021/acs.orglett.5c05455","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05455","url":null,"abstract":"Despite the broad utility of cyclic diaryl λ3-bromanes as aryne precursors for nucleophilic additions by heteroatom-based nucleophiles under mild basic conditions, their capacity to install arylchalcogen bonds in a regioselective manner is largely unexplored and challenging. The higher oxidative addition barrier of cyclic diaryl λ3-bromanes relative to their iodine analogues leads to transition-metal-catalyzed aryl–chalcogen bond formation requiring more forcing conditions, which decreases the regioselectivity. Moreover, the oxidizing character of hypervalent bromanes might be problematic. Herein, we disclose a photocatalytic strategy to achieve highly regioselective thiolation and selenylation of cyclic diaryl λ3-bromanes. This reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with a good functional group tolerance and excellent regioselectivity.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"50 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111256","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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