{"title":"A Silicon-Doped Nanographenic Bowl for Supramolecular Assembly with Fullerenes","authors":"Bo Yang, , , Yixun Sun, , , Jiale Hu, , , Muhua Chen, , , Xin Wang, , , Juan Fan, , , Huaming Sun, , , Jing Li*, , and , Junfa Wei*, ","doi":"10.1021/acs.orglett.5c03421","DOIUrl":"10.1021/acs.orglett.5c03421","url":null,"abstract":"<p >A silicon-doped nanographenic bowl, trisilasupersumanene <b>1</b>, was synthesized via a 3-fold palladium-catalyzed sila-annulation from the hexachlorinated trifluorenocoronene. Incorporating silole rings into the aromatic framework leads to new reduction waves in cyclic voltammetry and low-lying LUMO levels. The bowl <b>1</b> exhibits high binding affinity to fullerenes C<sub>60</sub> and C<sub>70</sub>, forming supramolecular complexes <b>1⊃C</b><sub><b>60</b></sub> and <b>(1)</b><sub><b>2</b></sub><b>⊃C</b><sub><b>70</b></sub> with unique packing arrangements. Notably, <b>(1)</b><sub><b>2</b></sub><b>⊃C</b><sub><b>70</b></sub> features a rare clam-like structure in the crystal, entirely different from its binding behavior in solution.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"11045–11051"},"PeriodicalIF":5.0,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084100","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}
{"title":"Aryl-Alkenylation and Aryl-Iodination of Strained C–C σ Bonds via Palladium Photoredox Catalysis","authors":"Shuaikang Li, , , Baoling Huang, , , Yunfeng Chen, , , Yingyu Yang, , , Tangji Chen, , , Ting Li, , , Qiaoyu Ou, , , Weigao Hu*, , and , Jia Zheng*, ","doi":"10.1021/acs.orglett.5c03373","DOIUrl":"10.1021/acs.orglett.5c03373","url":null,"abstract":"<p >Here, we present a Pd/blue-light-catalyzed strategy for the redox-neutral difunctionalization of bicyclo[1.1.0]butanes (BCBs). This mild protocol enables the rapid construction of iodinated and alkenylated 3-spirocyclobutyl oxindoles through strained C–C σ bond activation. Sensitive functional groups were tolerated, including hydroxyl, Bpin, and pyridine, as well as some drug structures. In our approach, C–I bond reductive elimination was more favored than β-H elimination due to the ring strain. The further derivatization of iodinated products proved its synthetic utility. This methodology complements avenues for hybrid palladium catalysis as well as the construction of functionalized spirocyclobutyl molecules.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"11027–11032"},"PeriodicalIF":5.0,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084099","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}
{"title":"Pd-Catalyzed Four-Component Cascade Cyclization of Alkynols, Aryl Iodides, CO, and Amines","authors":"Jiangui Zhao, , , Yonglin Shi, , , Dexi Yang, , , Jiaqi Xu, , , Meng Yang, , , Chunchun Zhang, , , Xueli Zheng*, , , Ruixiang Li, , , Haiyan Fu*, , , Weichao Xue*, , and , Hua Chen*, ","doi":"10.1021/acs.orglett.5c03282","DOIUrl":"10.1021/acs.orglett.5c03282","url":null,"abstract":"<p >Controlling selectivity and reaction pathways in multicomponent reactions for the synthesis of complex molecules from readily available starting materials is an attractive yet challenging goal in synthetic organic chemistry. Herein, we disclose a concise Pd-catalyzed four-component cyclization that enables the modular synthesis of dihydrofuran and pyrazoline scaffolds bearing quaternary carbon centers in high yields. The high-yielding nature, broad substrate scope, and successful late-stage modification of biologically relevant molecules collectively demonstrate the practicality of this method.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 38","pages":"10745–10753"},"PeriodicalIF":5.0,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145078355","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}
Organic LettersPub Date : 2025-09-18DOI: 10.1021/acs.orglett.5c03701
Jing Pang, , , Nan Cao, , , Ya-Shuang Dai, , , Xiaolei Huang, , , Yanli Liu, , , Bin Huang*, , and , Ya-Qiu Long*,
{"title":"Diversifiable Total Synthesis of Pleurotin Natural Products through Alternative Endgame Strategies Enabling Unprecedented C7/C8-Axial Functionalization","authors":"Jing Pang, , , Nan Cao, , , Ya-Shuang Dai, , , Xiaolei Huang, , , Yanli Liu, , , Bin Huang*, , and , Ya-Qiu Long*, ","doi":"10.1021/acs.orglett.5c03701","DOIUrl":"10.1021/acs.orglett.5c03701","url":null,"abstract":"<p >Pleurotin (<b>1</b>) and dihydropleurotinic acid (<b>2</b>) are antibiotic antitumor benzoquinone meroterpenoids, particularly as potent inhibitors of thioredoxin reductase (TrxR). However, producing new derivatives by semisynthesis is underexplored due to a limited number of functional group handles. Herein we report alternative endgame strategies for construction of the lactone F-ring in the asymmetric total synthesis of pleurotin natural products, harvesting C7-/axial C8-functionalized pleurotin analogs previously unavailable. Essentially, we deployed selective allylic oxidation for C7 functionalization and Tebbe olefination followed by hydroboration–oxidation delivering unprecedented C8-axial analogs from the advanced pentacyclic scaffold <b>7</b> accessible in preparative scale. These novel analogs exhibited notable cytotoxicity against TrxR-overexpressed human cancer cells, with C8-axially substituted analogue <b>23</b> showcasing 9- and 16.7-fold enhancement in the potency inhibiting TrxR enzyme relative to <b>1</b> and the positive control auranofin, respectively. This detoured endgame strategy enables access to diverse analogs that were previously inaccessible, expanding the chemical and biological space of pleurotin natural products for translational medicine applications.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"11137–11142"},"PeriodicalIF":5.0,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145083944","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}
{"title":"Engineering Tryptophan Halogenase RebH for Regioselective Halogenation of Phenolic Compounds","authors":"Yutian Jia, , , Wenhe Zhang, , , Qizhen Wang, , , Jiuming Zhang, , , Jingbo Wanchao, , , Jianxin Li, , , Bin Qin*, , , Xian Jia*, , and , Song You*, ","doi":"10.1021/acs.orglett.5c03448","DOIUrl":"10.1021/acs.orglett.5c03448","url":null,"abstract":"<p >Herein, we engineered tryptophan halogenase RebH using alanine scanning and the focused rational iterative site-specific mutagenesis (FRISM) strategy to expand its substrate scope toward phenolic compounds, particularly hydroxyquinolines and hydroxyisoquinolines, with excellent regioselectivity. The optimal mutant, 3-LSR/V80A/F111G, exhibited a 5-fold increase in catalytic activity and an 86.5-fold enhancement in catalytic efficiency (<i>k</i><sub>cat</sub>/<i>K</i><sub>m</sub>) for 6-hydroxyisoquinoline compared with the template 3-LSR. Furthermore, 3-LSR/V80A/F111G enabled the synthesis of 5-bromo-6-hydroxyisoquinoline on a milligram-scale with >99.9% conversion and 84.3% isolated yield.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 38","pages":"10862–10867"},"PeriodicalIF":5.0,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077894","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}
{"title":"Multicomponent Synthesis of Isoquinuclidines via Pd-Catalyzed Selective Dechlorination","authors":"Qixin Zhou, , , Guocong Zhang, , , Yingqi Lan, , , Ting Long, , , Leixing Du, , , Tiancen Bian, , , Liejin Zhou*, , and , Zuxiao Zhang*, ","doi":"10.1021/acs.orglett.5c03136","DOIUrl":"10.1021/acs.orglett.5c03136","url":null,"abstract":"<p >We report a visible-light palladium-catalyzed multicomponent reaction enabling efficient synthesis of 2-azabicyclo[2.2.2]octenes via a multicomponent coupling of cyclic 1,3-dienes, <i>gem</i>-dichloroalkanes, and amines. Mechanistic studies indicate a radical pathway with selective dechlorination and high 1,4-syn diastereoselectivity. This mild, efficient method provides sp<sup>3</sup>-rich bicyclic scaffolds amenable to further derivatization. Its utility is demonstrated in concise syntheses of bioactive alkaloids, including deethylibogamine and Rauwolfia analogues, highlighting its potential for complex molecule construction in medicinal chemistry.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 38","pages":"10670–10675"},"PeriodicalIF":5.0,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145071931","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}
Organic LettersPub Date : 2025-09-17DOI: 10.1021/acs.orglett.5c02589
Emmanouil Broumidis, , , Christopher G. Thomson, , , Brendan Gallagher, , , Lia Sotorríos, , , Kenneth G. McKendrick, , , Stuart A. Macgregor*, , , Martin J. Paterson, , , Janet E. Lovett, , , Gareth O. Lloyd, , , Georgina M. Rosair, , , Andreas S. Kalogirou, , , Panayiotis A. Koutentis*, , and , Filipe Vilela*,
{"title":"Correction to “The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides”","authors":"Emmanouil Broumidis, , , Christopher G. Thomson, , , Brendan Gallagher, , , Lia Sotorríos, , , Kenneth G. McKendrick, , , Stuart A. Macgregor*, , , Martin J. Paterson, , , Janet E. Lovett, , , Gareth O. Lloyd, , , Georgina M. Rosair, , , Andreas S. Kalogirou, , , Panayiotis A. Koutentis*, , and , Filipe Vilela*, ","doi":"10.1021/acs.orglett.5c02589","DOIUrl":"10.1021/acs.orglett.5c02589","url":null,"abstract":"","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 38","pages":"10936"},"PeriodicalIF":5.0,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.orglett.5c02589","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145078518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Visible-Light-Driven [2+2] Cycloaddition of Coumarins with Diverse Olefins Using a 4CzIPN Photosensitizer: Application to the Total Synthesis of (±)-Lindleyanin","authors":"Chun-Hong Long, , , Ya-Peng Zuo, , , Chui-Chang Kong, , , Zhao-Nan Cai*, , and , Hong-Bo Qin*, ","doi":"10.1021/acs.orglett.5c03393","DOIUrl":"10.1021/acs.orglett.5c03393","url":null,"abstract":"<p >Cyclobutane scaffolds represent essential structural motifs in bioactive natural products; however, their synthesis often requires high-energy ultraviolet radiation or costly transition metal catalysts. Herein, we present a sustainable metal-free photosensitized energy transfer strategy for the [2+2] cycloaddition of coumarins with diverse olefins under visible-light irradiation. Employing the organic photocatalyst 4CzIPN in the environmentally benign solvent dimethyl carbonate (DMC), the reaction proceeds efficiently at ambient temperature using a 25 W blue LED, generating cyclobutane-fused chromones in 31–89% yields. The methodology demonstrates an exceptional substrate scope, tolerating diverse styrenes, aliphatic olefins, cycloalkenes (up to eight-membered rings), and heterocycles like benzothiophene. Notably, gram-scale reactions retain a high efficiency, providing the cycloaddition product in 72% yield. Furthermore, implementation of this strategy as a key transformation facilitated the first seven-step total synthesis of the cyclobutane-containing natural product (±)-lindleyanin (5/6/4/6/6/5-fused polycyclic system), underscoring its utility for constructing complex molecular architectures.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"11038–11044"},"PeriodicalIF":5.0,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073068","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}
{"title":"Palladium-Catalyzed Suzuki–Miyaura Couplings of Glycal Boronates with Aryl Thianthrenium Salts for the Synthesis of C-Aryl Glycals","authors":"Yu Zhang, , , Chengyang Guan, , , Mingjie Zeng, , , Qian Wang, , , Hong Liu*, , and , Jiang Wang*, ","doi":"10.1021/acs.orglett.5c03390","DOIUrl":"10.1021/acs.orglett.5c03390","url":null,"abstract":"<p >Aryl <i>C</i>-glycosides represent key structure motifs in numerous natural products and pharmaceuticals. Here, we report a palladium-catalyzed Suzuki–Miyaura cross-coupling reaction between glycal boronates and aryl thianthrenium salts under mild conditions, enabling the synthesis of <i>C</i>-aryl glycals. This method features broad substrate scope, excellent functional group tolerance, and operational simplicity. Furthermore, the synthetic utility of this strategy is demonstrated through late-stage functionalization of structurally complex drug molecules, underscoring its potential for medicinal chemistry applications.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 38","pages":"10778–10784"},"PeriodicalIF":5.0,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145071930","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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