Pub Date : 2026-01-30DOI: 10.1021/acs.orglett.5c04617
Zi-Kui Liu,Yun-Kun Su,Cong-Fang Cheng,Hao Dong,Yi Wei,Xiao-Qiang Hu,You-Quan Zou
Herein, we report a ball milling technique for the regioselective hydrophosphinylation of acrylamides and enamides, utilizing readily available Ph2PCl as the phosphine source and H2O as an additive under metal-free and toxic solvent-free conditions. Michael-type and Markovnikov hydrophosphinylation reactions have been achieved for acrylamides and enamides, respectively. The reaction features broad substrate scope, sustainable conditions and high atom economy, facilitating the rapid assembly of structurally diverse amide-based phosphine oxides in useful to good yields.
{"title":"Mechanochemistry-Enhanced Regioselective Hydrophosphinylation of Acrylamides and Enamides.","authors":"Zi-Kui Liu,Yun-Kun Su,Cong-Fang Cheng,Hao Dong,Yi Wei,Xiao-Qiang Hu,You-Quan Zou","doi":"10.1021/acs.orglett.5c04617","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c04617","url":null,"abstract":"Herein, we report a ball milling technique for the regioselective hydrophosphinylation of acrylamides and enamides, utilizing readily available Ph2PCl as the phosphine source and H2O as an additive under metal-free and toxic solvent-free conditions. Michael-type and Markovnikov hydrophosphinylation reactions have been achieved for acrylamides and enamides, respectively. The reaction features broad substrate scope, sustainable conditions and high atom economy, facilitating the rapid assembly of structurally diverse amide-based phosphine oxides in useful to good yields.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"8 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073293","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 : 2026-01-30DOI: 10.1021/acs.orglett.5c05391
Maria-Aikaterini Giannakaki,Marios Zingiridis,Konstantinos G Froudas,Constantinos G Neochoritis
We present mAUCy (modified Asinger-Ugi cyclization), a scalable three-layer strategy enabling rapid synthesis of diverse thiazolo hydantoins and diketopiperazines. Beginning from 3-thiazolines via a modified Asinger reaction, followed by an Ugi-Joullié multicomponent reaction and base-induced annulation, the method delivers complex compounds in less than 3 h. Operable on a multigram scale without chromatography, it allows telescoped one-pot processing, a broad substrate scope, and late-stage modifications. Single-crystal analysis confirmed the scaffold structures.
{"title":"A Three-Layer Transformation Strategy toward Functionalized Fused Hydantoins and Diketopiperazines.","authors":"Maria-Aikaterini Giannakaki,Marios Zingiridis,Konstantinos G Froudas,Constantinos G Neochoritis","doi":"10.1021/acs.orglett.5c05391","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05391","url":null,"abstract":"We present mAUCy (modified Asinger-Ugi cyclization), a scalable three-layer strategy enabling rapid synthesis of diverse thiazolo hydantoins and diketopiperazines. Beginning from 3-thiazolines via a modified Asinger reaction, followed by an Ugi-Joullié multicomponent reaction and base-induced annulation, the method delivers complex compounds in less than 3 h. Operable on a multigram scale without chromatography, it allows telescoped one-pot processing, a broad substrate scope, and late-stage modifications. Single-crystal analysis confirmed the scaffold structures.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"182 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073299","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 : 2026-01-30DOI: 10.1021/acs.orglett.5c05026
Yin-Ying Luo,Shu-Yun Zhang,Yan-Xin Jiang,Song-Bai Tang,Jia-Hao Ruan,Jing Su
Under mild conditions, uranyl nitrate catalyzed C(sp3)-center/azole coupling without external additives, offering a broad substrate scope and high yields (up to 95%). The method was further validated under sunlight and in scale-up experiments, highlighting its industrial potential. Experimental and theoretical studies show that uranyl nitrate acts via both hydrogen-atom transfer (HAT) and non-HAT concerted proton-electron transfer mechanisms. This approach provides a green, efficient protocol for C(sp3)-azole bond formation.
{"title":"Uranyl-Enabled Photocatalytic C(sp3)-H Functionalization with Azoles.","authors":"Yin-Ying Luo,Shu-Yun Zhang,Yan-Xin Jiang,Song-Bai Tang,Jia-Hao Ruan,Jing Su","doi":"10.1021/acs.orglett.5c05026","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05026","url":null,"abstract":"Under mild conditions, uranyl nitrate catalyzed C(sp3)-center/azole coupling without external additives, offering a broad substrate scope and high yields (up to 95%). The method was further validated under sunlight and in scale-up experiments, highlighting its industrial potential. Experimental and theoretical studies show that uranyl nitrate acts via both hydrogen-atom transfer (HAT) and non-HAT concerted proton-electron transfer mechanisms. This approach provides a green, efficient protocol for C(sp3)-azole bond formation.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"30 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073297","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 : 2026-01-30DOI: 10.1021/acs.orglett.5c04654
Vitor A S Almodovar,Gonçalo F Oliveira,Nuno R Candeias,Filipe A Almeida Paz,Augusto C Tomé
We report an unprecedented reaction of a diketopyrrolopyrrole (DPP) with primary and secondary amines that results in the ring-opening of the core with loss of its fluorescence. The various characterization techniques used in this study, such as X-ray diffraction, NMR spectroscopy, mass spectrometry, and UV-vis analysis, warrant accurate identification of the structures of the newly synthesized compounds. DFT studies were also performed in order to understand the mechanism associated with this reaction.
{"title":"Divergent Reactivity of Diketopyrrolopyrroles: Ring-Opening with Amines.","authors":"Vitor A S Almodovar,Gonçalo F Oliveira,Nuno R Candeias,Filipe A Almeida Paz,Augusto C Tomé","doi":"10.1021/acs.orglett.5c04654","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c04654","url":null,"abstract":"We report an unprecedented reaction of a diketopyrrolopyrrole (DPP) with primary and secondary amines that results in the ring-opening of the core with loss of its fluorescence. The various characterization techniques used in this study, such as X-ray diffraction, NMR spectroscopy, mass spectrometry, and UV-vis analysis, warrant accurate identification of the structures of the newly synthesized compounds. DFT studies were also performed in order to understand the mechanism associated with this reaction.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"7 6 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089163","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 : 2026-01-30DOI: 10.1021/acs.orglett.6c00199
Yao Yao,Ming-Liang Shi,Xin-Yue Fan,Ke Xu,Kun Li,Xiao-Qi Yu,Shan-Yong Chen,Na Wang
The development of photoenzymatic non-natural reactions facilitates the synthesis of challenging high-value-added chiral compounds. However, this approach typically requires enzyme engineering to enhance both the catalytic activity and selectivity. Herein, we report a synergistic photoenymatic system comprising wild-type GluER and exogenous Ru(bpy)3Cl2·6H2O that enables the photoenzymatic enantioselective hydroalkylation of olefins. In this system, Ru(bpy)3Cl2·6H2O replaces protein engineering, driving an efficient catalytic cycle. The radical initiation was by electron transfer between excited Ru(bpy)3Cl2·6H2O and an in situ-formed ternary electron donor-acceptor (EDA) complex. This synergistic photo/biocatalytic system decreases the time-consuming and labor-intensive nature while providing an environmentally friendly methodology for chemical synthesis.
{"title":"Synergistic Photoenzymatic Catalysis Enables Enantioselective Synthesis of γ-Amides via a Ternary Electron Donor-Acceptor Complex.","authors":"Yao Yao,Ming-Liang Shi,Xin-Yue Fan,Ke Xu,Kun Li,Xiao-Qi Yu,Shan-Yong Chen,Na Wang","doi":"10.1021/acs.orglett.6c00199","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00199","url":null,"abstract":"The development of photoenzymatic non-natural reactions facilitates the synthesis of challenging high-value-added chiral compounds. However, this approach typically requires enzyme engineering to enhance both the catalytic activity and selectivity. Herein, we report a synergistic photoenymatic system comprising wild-type GluER and exogenous Ru(bpy)3Cl2·6H2O that enables the photoenzymatic enantioselective hydroalkylation of olefins. In this system, Ru(bpy)3Cl2·6H2O replaces protein engineering, driving an efficient catalytic cycle. The radical initiation was by electron transfer between excited Ru(bpy)3Cl2·6H2O and an in situ-formed ternary electron donor-acceptor (EDA) complex. This synergistic photo/biocatalytic system decreases the time-consuming and labor-intensive nature while providing an environmentally friendly methodology for chemical synthesis.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"17 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089159","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 : 2026-01-29DOI: 10.1021/acs.orglett.5c05427
Xinmin Huang,Xu Han,Chuang Niu,Wen-Jie Qiu,Zhiwei Xu,Hai-Bin Zhou,Zheng-Chun Yin,Guan-Wu Wang
Novel and challenging [60]fullerene (C60)-fused ζ-lactones, containing an eight-membered ring, have been successfully synthesized via palladium-catalyzed annulations of C60 with 2-arylbenzoic acids. This approach employs a carboxyl-directed C-H activation strategy to facilitate lactone formation. The formed ζ-lactones undergo an unprecedented deoxygenative skeletal rearrangement in the presence of triflic anhydride to generate C60-fluorenone conjugates. The assigned structures were confirmed by single-crystal X-ray diffraction. The C60-fused ζ-lactones can be further electrochemically transformed into 1,2-hydrofullerenes. In addition, a representative ζ-lactone was efficiently employed as the third component in organic solar cells, resulting in an improvement in device performance.
{"title":"[60]Fullerene-Fused ζ-Lactones: Synthesis and Further Transformations.","authors":"Xinmin Huang,Xu Han,Chuang Niu,Wen-Jie Qiu,Zhiwei Xu,Hai-Bin Zhou,Zheng-Chun Yin,Guan-Wu Wang","doi":"10.1021/acs.orglett.5c05427","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05427","url":null,"abstract":"Novel and challenging [60]fullerene (C60)-fused ζ-lactones, containing an eight-membered ring, have been successfully synthesized via palladium-catalyzed annulations of C60 with 2-arylbenzoic acids. This approach employs a carboxyl-directed C-H activation strategy to facilitate lactone formation. The formed ζ-lactones undergo an unprecedented deoxygenative skeletal rearrangement in the presence of triflic anhydride to generate C60-fluorenone conjugates. The assigned structures were confirmed by single-crystal X-ray diffraction. The C60-fused ζ-lactones can be further electrochemically transformed into 1,2-hydrofullerenes. In addition, a representative ζ-lactone was efficiently employed as the third component in organic solar cells, resulting in an improvement in device performance.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"30 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073305","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 : 2026-01-29DOI: 10.1021/acs.orglett.5c05153
G Sudhakar Reddy,E J Corey
Reported herein are new results on the mechanism of action and scope of a recently discovered process for enantio- and position-selective epoxidation of C═C using a novel chiral Mn(II) catalyst at 3 mol %. A novel axially symmetric cationic Mn(V)-oxo complex has been found to deliver oxygen to a double bond with a strong and predictable enantiofacial preference. The method has been demonstrated for a variety of mono- and trisubstituted olefins. The rate-limiting step is not formation of the Mn(V)-oxo intermediate but transfer of oxygen from it to the olefin operating under the Curtin-Hammett principle.
{"title":"Experimental Support for a Chiral Pentacoordinate, Axially Symmetric Cationic Mn(V)-Oxo Complex as the Key Reactant in the Highly Enantioselective Catalytic Epoxidation of Olefins.","authors":"G Sudhakar Reddy,E J Corey","doi":"10.1021/acs.orglett.5c05153","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05153","url":null,"abstract":"Reported herein are new results on the mechanism of action and scope of a recently discovered process for enantio- and position-selective epoxidation of C═C using a novel chiral Mn(II) catalyst at 3 mol %. A novel axially symmetric cationic Mn(V)-oxo complex has been found to deliver oxygen to a double bond with a strong and predictable enantiofacial preference. The method has been demonstrated for a variety of mono- and trisubstituted olefins. The rate-limiting step is not formation of the Mn(V)-oxo intermediate but transfer of oxygen from it to the olefin operating under the Curtin-Hammett principle.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"15 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073306","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 : 2026-01-29DOI: 10.1021/acs.orglett.5c05307
Jun Wu,Wei-Chen Chen,Bowei Wen,Jing Chen,Zhuoyue Yang,Ke Lu,Zhaoxin Yao,Zhicheng Guo,Hui Qiu,Zixin Deng,Ning Li,You-Sheng Cai,Kui Hong
Genome mining of Talaromyces radicus WHUF04045 identified two unusual nrPKSs (Tr4942 and Tr2381) with distinct release mechanisms, whose precursor competition was revealed by multiomics, gene deletion, and heterologous expression. Deletion of Tr4942 activated nine new chromone derivatives (1-9) and four new naphthoquinone derivatives (11-14), which displayed significant pro-angiogenic and anti-inflammatory activities, with compound 8 showing significant anti-inflammatory effects via modulation of the NF-κB signaling pathway.
{"title":"Metabolic Competition between Non-reducing Polyketide Synthases Drives Hidden Chemodiversity in Deep-Sea Fungus Talaromyces radicus.","authors":"Jun Wu,Wei-Chen Chen,Bowei Wen,Jing Chen,Zhuoyue Yang,Ke Lu,Zhaoxin Yao,Zhicheng Guo,Hui Qiu,Zixin Deng,Ning Li,You-Sheng Cai,Kui Hong","doi":"10.1021/acs.orglett.5c05307","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05307","url":null,"abstract":"Genome mining of Talaromyces radicus WHUF04045 identified two unusual nrPKSs (Tr4942 and Tr2381) with distinct release mechanisms, whose precursor competition was revealed by multiomics, gene deletion, and heterologous expression. Deletion of Tr4942 activated nine new chromone derivatives (1-9) and four new naphthoquinone derivatives (11-14), which displayed significant pro-angiogenic and anti-inflammatory activities, with compound 8 showing significant anti-inflammatory effects via modulation of the NF-κB signaling pathway.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"6 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073312","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 : 2026-01-29DOI: 10.1021/acs.orglett.5c05338
Shan Jiang,Xiaoqi Yang,Xiao-Le Han,Yi Wei,Xiao-Qiang Hu
Herein, we demonstrate a ring-strain-driven annulation of cyclopropenones with hydrazones via simple phosphine catalysis, providing an efficient route to structurally diverse 1,3,4-oxadiazolines and spiro-1,3,4-oxadiazolines under mild conditions. The reaction proceeds through the formation of a reactive α-ketenyl phosphorus ylide intermediate, generated by the interaction of cyclopropenone with a nucleophilic phosphine catalyst. Notably, an intriguing acyl group migration-mediated [3+2] annulation is observed with hydrazones derived from linear ketones, while a ring-opening addition/cyclization cascade takes place with cyclic hydrazones.
{"title":"Ring-Strain-Driven Annulation of Cyclopropenones with Hydrazones via Nucleophilic Phosphine Catalysis.","authors":"Shan Jiang,Xiaoqi Yang,Xiao-Le Han,Yi Wei,Xiao-Qiang Hu","doi":"10.1021/acs.orglett.5c05338","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05338","url":null,"abstract":"Herein, we demonstrate a ring-strain-driven annulation of cyclopropenones with hydrazones via simple phosphine catalysis, providing an efficient route to structurally diverse 1,3,4-oxadiazolines and spiro-1,3,4-oxadiazolines under mild conditions. The reaction proceeds through the formation of a reactive α-ketenyl phosphorus ylide intermediate, generated by the interaction of cyclopropenone with a nucleophilic phosphine catalyst. Notably, an intriguing acyl group migration-mediated [3+2] annulation is observed with hydrazones derived from linear ketones, while a ring-opening addition/cyclization cascade takes place with cyclic hydrazones.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"8 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073302","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}
Here we report a highly enantioselective cycloaddition of 1,6-diynes and alkenes mediated by cobalt/photoredox cooperative catalysis. This transformation requires a chiral monodentate phosphine ligand, which is rarely applied in such reactions because of its limited stereocontrol. DFT studies reveal that the ligand controls metal-centered chirality, enabling the synthesis of multisubstituted cyclohexadienes with excellent enantioselectivity.
{"title":"Asymmetric Cycloaddition of 1,6-Diynes with Alkenes Enabled by Ligand-to-Metal Chirality Transfer in Cobalt/Photoredox Cooperative Catalysis.","authors":"Takeshi Yasui,Keiji Yamada,Yuki Ishikawa,Kotoko Nakagawa,Rinto Fujii,Yoshihiko Yamamoto","doi":"10.1021/acs.orglett.5c05365","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05365","url":null,"abstract":"Here we report a highly enantioselective cycloaddition of 1,6-diynes and alkenes mediated by cobalt/photoredox cooperative catalysis. This transformation requires a chiral monodentate phosphine ligand, which is rarely applied in such reactions because of its limited stereocontrol. DFT studies reveal that the ligand controls metal-centered chirality, enabling the synthesis of multisubstituted cyclohexadienes with excellent enantioselectivity.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"34 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073304","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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