{"title":"Catalyst-controlled chemodivergent C–H functionalization of 2-pyridylthiophenes with allylic alcohols","authors":"Guibin Wan, Qiang Zhang, Ying Liu, Haowei Zeng, Taoyuan Liang, Shuangliang Zhao, Zhuan Zhang","doi":"10.1039/d6qo00441e","DOIUrl":"10.1039/d6qo00441e","url":null,"abstract":"<div><div>A catalyst-controlled chemodivergent C–H functionalization of 2-pyridylthiophenes using allylic alcohols as versatile coupling partners is reported. Modulation of the catalytic system enables selective access to two distinct reaction pathways from identical substrates. A Rh-based catalyst promotes redox-neutral C–H alkylation to afford β-aryl ketones <em>via</em> C–H activation, alkene insertion, and subsequent tautomerization, whereas a Co-based system enables dehydrative C–H allylation through β-hydroxide elimination, retaining the olefinic moiety. This protocol achieves regioselective C3-functionalization in a step- and atom-economical manner, overcoming the inherent chemoselectivity challenges of free allylic alcohols and providing efficient access to structurally diverse heteroaromatics.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4118-4123"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503426","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}
Jaime Tostado, Alex Hipólito, Jaime Mateos-Gil, Raúl Losantos, Diego Sampedro, Manuel A. Fernández-Rodríguez
{"title":"Synthesis of fluorescent cyclopentene-fused-phenanthrenes via boron trifluoride-promoted cascade cationic cyclization","authors":"Jaime Tostado, Alex Hipólito, Jaime Mateos-Gil, Raúl Losantos, Diego Sampedro, Manuel A. Fernández-Rodríguez","doi":"10.1039/d6qo00325g","DOIUrl":"10.1039/d6qo00325g","url":null,"abstract":"<div><div>A metal-free, BF<sub>3</sub>-promoted cascade cyclization of biaryl-embedded enynones with nitriles is disclosed, enabling rapid access to amide-functionalized cyclopentene-fused phenanthrenes under mild conditions. The transformation is initiated by electrophilic activation of the enone, which triggers two consecutive intramolecular cyclizations followed by a Ritter-type reaction. This process builds two new C–C bonds, one C–N bond, and one CO bond, affording structurally intricate tetracyclic frameworks with high efficiency. In contrast to previously reported related cyclizations, this strategy uniquely exploits both electrophilic sites of the enone and incorporates external nucleophiles beyond water, thereby substantially expanding the synthetic scope of enynone-based cationic cascade processes. The protocol exhibits broad applicability to enynone substrates and accommodates a diverse array of nitriles, underscoring its synthetic versatility. Mechanistic studies, supported by DFT calculations and experimental evidence, elucidate the origins of reactivity and selectivity. Notably, the resulting polycyclic products display remarkable photophysical properties, with solid-state fluorescence quantum yields of up to 0.35, highlighting their potential as fluorescent materials and molecular probes.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 3952-3959"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503365","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}
Hongliang Ran, Junyu Zhou, Lingyu Huang, Kai Tao, Shiqing Li, Jinhua Wang
{"title":"Site-selective [4 + 2] and [4 + 3] annulations of arylboronic acids with cyclic diaryliodoniums for polycyclic arene synthesis","authors":"Hongliang Ran, Junyu Zhou, Lingyu Huang, Kai Tao, Shiqing Li, Jinhua Wang","doi":"10.1039/d6qo00459h","DOIUrl":"10.1039/d6qo00459h","url":null,"abstract":"<div><div>A facile access to functionalized triphenylenes through tandem Suzuki–Miyaura and intramolecular C–C coupling between arylboronic acids and cyclic diaryliodonium salts is disclosed. More importantly, this protocol can be extended to large-sized boronic acids involving naphthalene, anthracene, pyrene, triphenylene, dibenzo[<em>b</em>,<em>d</em>]thiophene, and carbazole units bearing two competitive C(sp<sup>2</sup>)–H bonds, and all these cases show good α-selectivity. This α-selective [4 + 2] annulation provides a fast access to π-extended polycyclic arenes including [4]- and [5]carbohelicenes as well as their aza-/thia-hybrids. Moreover, the double annulation version on diboronic acids is presented as an efficient and fast route toward (helical) nanographenes. In addition, a selective Suzuki coupling and N–H activation cascade has been realized through the [4 + 3] annulation of (9<em>H</em>-carbazol-1-yl)boronic acids and cyclic iodoniums, providing nonalternant molecules bearing N-doped pentagon–heptagon pairs in good yields.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 3969-3975"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503366","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}
{"title":"Modular and stereoselective synthesis of Si-/Ge-glycosides via palladium-catalyzed bis-silylation and bis-germanylation of glycals","authors":"Weiwei Lv, Xueting Zhu, Wendong Peng, Dong Zhang, Youlin Yan, Jing Lu, Wanying Yang, Qiaoyun Li, Guolin Cheng","doi":"10.1039/d6qo00406g","DOIUrl":"10.1039/d6qo00406g","url":null,"abstract":"<div><div>In this study, we report an efficient palladium-catalyzed C–H silylation and germanylation that enables rapid modular and stereoselective access to various highly decorated Si- and Ge-glycosides. The protocol employs hexamethyldisilane and hexamethyldigermane as the model bis-silylation and bis-germanylation reagents, respectively, with NBE derivatives as the <em>ortho</em>-C–H activator. Additionally, a series of Si-glycosides bearing one (<em>Z</em>)-β-substituted vinylsilane and Ge-glycosides bearing one (<em>Z</em>)-β-substituted vinylgermane were also obtained under mild conditions by employing 2,3-dicarbomethoxy-7-oxanorbornadiene (ONBD) as both a switch and an ethylene surrogate. This work pioneers the Catellani strategy in the assembly of Si- and Ge-glycosides, establishing an efficient platform for bioactive glycomimetic development and advancing carbohydrate-based drug discovery.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4102-4108"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503379","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}
Qichao Zhang, Fang Zhang, Qi Wu, Lin He, Zhihua Cai, Guangfen Du
{"title":"Imidazolium-dithiocarboxylate zwitterion-catalyzed synthesis of fully substituted spiro-glutarimides via [3 + 3] annulation of cyclopropenones","authors":"Qichao Zhang, Fang Zhang, Qi Wu, Lin He, Zhihua Cai, Guangfen Du","doi":"10.1039/d6qo00157b","DOIUrl":"10.1039/d6qo00157b","url":null,"abstract":"<div><div>An organocatalytic [3 + 3] annulation reaction of cyclopropenones and cyclic β-ketoamides has been reported for the synthesis of fully substituted spiro-glutarimides. Under the catalysis of imidazolium-dithiocarboxylate zwitterions (NHC·CS<sub>2</sub>), cyclopropenones react with cyclic ketoamides through a tandem ring opening/intermolecular nucleophilic substitution/intramolecular nucleophilic addition/tautomerization process to afford a diverse range of spirocyclic glutarimide derivatives containing one all-carbon quaternary spirocenter in high yields with excellent diastereoselectivity. The reaction can be scaled up easily and the stable NHC·CS<sub>2</sub> zwitterion catalyst can be recovered and reused at least four times.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4124-4130"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503427","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}
{"title":"Electrochemically enabled C7 functionalization of quinolines from o-propynolanilines: divergent access to 4,7-dichloro and 4-chloro-7-alkyl (aryl) quinolines","authors":"Xin Feng, Qiuqin He, Renhua Fan, Jiwen He","doi":"10.1039/d5qo01687h","DOIUrl":"10.1039/d5qo01687h","url":null,"abstract":"<div><div>The regioselective functionalization of the C7 position of quinoline remains a formidable challenge due to its inherent electronic deactivation. Herein, we report an electrochemical strategy that enables the divergent synthesis of valuable C7-chlorinated and alkylated (arylated) quinolines from simple <em>ortho</em>-propynolaniline precursors. This method leverages electrooxidative dearomatization to generate key cyclohexadienimine intermediates, which undergo two distinct pathways dictated by the <em>para</em>-substituent: TMSCl-mediated cascade chlorination/cyclization delivers 4,7-dichloroquinolines, while substrates bearing <em>para</em>-alkyl/aryl groups (R<sup>2</sup> ≠ Me) undergo an aromatization-driven [1,2]-σ migration to furnish 4-chloro-7-alkyl/arylquinolines with high selectivity. This approach bypasses the reliance on pre-functionalized <em>meta</em>-chloroaniline substrates and hazardous chlorinating agents, operating under mild conditions. Gram-scale synthesis and further derivatizations highlight the practical utility of this method, offering a versatile and sustainable platform for constructing complex quinoline architectures.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4037-4044"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146134069","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}
{"title":"Photocatalytic defluoroalkylation of trifluoromethylaromatics with arylethylenes","authors":"Shiyong Guan, Yiteng Zheng, Zihan Cai, Yuegang Chen","doi":"10.1039/d6qo00541a","DOIUrl":"10.1039/d6qo00541a","url":null,"abstract":"<div><div>We present a novel fluorine atom transfer technique for the selective functionalization of robust C–F bonds in trifluoromethylated aromatic compounds. This approach employs neutral boron radicals to generate aryl difluoromethyl radicals through a C–F cleavage process. These radicals engage in highly effective intermolecular coupling with aryl alkenes throughout the defluoroalkylation process. This mild, catalytic reaction system accommodates a diverse array of substrates, producing difluoroalkyl structures of medicinal importance with total regioselectivity.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4064-4069"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503375","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}
Ryu Yamasaki, Yuta Nozaka, Ami Nagai, Ai Ito, Masatoshi Kawahata, Iwao Okamoto
{"title":"Conformational features of N-trifluoromethyl amides and thioamides","authors":"Ryu Yamasaki, Yuta Nozaka, Ami Nagai, Ai Ito, Masatoshi Kawahata, Iwao Okamoto","doi":"10.1039/d6qo00428h","DOIUrl":"10.1039/d6qo00428h","url":null,"abstract":"<div><div>We investigated the structural and conformational features of <em>N</em>-trifluoromethyl (<em>N</em>-CF<sub>3</sub>) (thio)amides using X-ray and VT-NMR analyses. These compounds showed lower rotational barriers and generally reduced <em>cis</em> populations compared with their <em>N</em>-methyl analogues. <em>N</em>-CF<sub>3</sub> thioamides did not prefer <em>cis</em> conformations in solution or the crystalline state, while computational studies suggest that the electronic effect of CF<sub>3</sub> such as the attenuation of the negative electrostatic potential on the thiocarbonyl sulfur also plays a role. These findings should be helpful in the design of new fluorinated functional molecules.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4031-4036"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503284","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}
{"title":"Pd-catalyzed site-selective dehydrogenative alkenyl etherification of tyrosine residues in peptides and proteins","authors":"Xia Liu, Wei Zeng, Jianjun Zhang, Peng Wang, Neeli Satyanarayana, Qing Zhu","doi":"10.1039/d6qo00358c","DOIUrl":"10.1039/d6qo00358c","url":null,"abstract":"<div><div>We report a palladium-catalyzed selective cross-coupling alkenyl etherification of the C(sp<sup>2</sup>)–O bond in tyrosine side chains, enabling the synthesis of diverse tyrosine-derived alkenyl ethers in moderate to good yields. This transformation provides a convenient strategy for introducing functional groups into peptides and proteins.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 3900-3908"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503387","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}
{"title":"Synergistic interplay between ligand- and metal-centered chirality in iridium-catalyzed enantioselective C(sp3)–H borylation of cyclopropanols","authors":"Xueyuan Yan, Genping Huang","doi":"10.1039/d6qo00471g","DOIUrl":"10.1039/d6qo00471g","url":null,"abstract":"<div><div>Density functional theory calculations were performed to investigate the Ir/CBL-catalyzed C(sp<sup>3</sup>)–H borylation of cyclopropanols. The computations indicate that the reaction follows an Ir(<span>iii</span>)/Ir(<span>v</span>) catalytic cycle with six- and seven-coordinate intermediates, involving both Λ- and Δ-configured iridium species. The metal-centered chirality plays a key role in determining the enantioselectivity. The <em>ortho</em>-substituent on the <em>N</em>-aryl group of the ligand has a significant impact on the Δ-configured C(sp<sup>3</sup>)–B reductive elimination, which can modulate the relative reactivity of the Λ- and Δ-configured intermediates, accounting for the experimentally observed enantioselectivities. The results reveal a synergistic interplay between ligand- and metal-centered chirality, which together dictate the observed enantioselectivity.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 3915-3922"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503428","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}