Organic LettersPub Date : 2024-12-23DOI: 10.1021/acs.orglett.4c04495
Ivan Borkovic, Zorana Ferjancic, Filip Bihelovic
{"title":"A Formal 1,2-Stevens Rearrangement of Thioester Ylides as a Single-Atom Molecular Editing Tool","authors":"Ivan Borkovic, Zorana Ferjancic, Filip Bihelovic","doi":"10.1021/acs.orglett.4c04495","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04495","url":null,"abstract":"A rhodium-catalyzed reaction of thioesters with diazo reagents was recognized as a powerful and unprecedented tool for single-atom molecular editing by the insertion of a single carbon atom into the C(O)─S thioester bond, thereby leading to various α-thioketones possessing a quaternary carbon atom. A selective and precise defunctionalization of the polyfunctionalized products further demonstrated the synthetic utility of the reaction for the synthesis of more common structural classes of compounds.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"1 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880134","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 : 2024-12-23DOI: 10.1021/acs.orglett.4c03992
Hui-Lin Hu, Siqiang Fang, Xingjie Luo, Jiajia He, Jia-Hong Wu, Zhishan Su, Zhipeng Xu, Tianli Wang
{"title":"Organocatalytic Enantioselective Arylation to Access Densely Aryl-Substituted P-Stereogenic Centers","authors":"Hui-Lin Hu, Siqiang Fang, Xingjie Luo, Jiajia He, Jia-Hong Wu, Zhishan Su, Zhipeng Xu, Tianli Wang","doi":"10.1021/acs.orglett.4c03992","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03992","url":null,"abstract":"Although methods for synthesizing chiral phosphorus scaffolds are available, the potential of this molecular chirality remains largely unexplored. Herein, we present a remote desymmetrization of prochiral biaryl phosphine oxides through an organocatalytic asymmetric arylation. This metal-free approach enables the efficient synthesis of a wide range of densely functionalized P(V)-stereogenic compounds with good to excellent yields and satisfactory enantioselectivities. Mechanistic studies reveal that hydrogen bonding and ion-pairing interactions are crucial for achieving precise stereocontrol in this transformation.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"31 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874513","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 : 2024-12-23DOI: 10.1021/acs.orglett.4c04444
Chong-Yang Shi, Xuan Wang, Xin Liu, Zu-Hui Ai, Shuai Xiong, Long-Wu Ye, Bo Zhou, Xin-Qi Zhu
{"title":"Copper-Catalyzed [2,3]-Sigmatropic Rearrangement of Azide–Ynamides via Selenium Ylides","authors":"Chong-Yang Shi, Xuan Wang, Xin Liu, Zu-Hui Ai, Shuai Xiong, Long-Wu Ye, Bo Zhou, Xin-Qi Zhu","doi":"10.1021/acs.orglett.4c04444","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04444","url":null,"abstract":"A copper-catalyzed [2,3]-sigmatropic rearrangement of azide–ynamides via selenium ylides is disclosed, which leads to the practical and divergent synthesis of a variety of tricyclic heterocycles bearing a quaternary carbon stereocenter in generally moderate to excellent yields. Significantly, this method represents the first [2,3]-sigmatropic rearrangement of the selenium ylide based on alkynes and an unprecedented [2,3]-sigmatropic rearrangement via α-imino copper carbenes.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"475 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874515","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 : 2024-12-23DOI: 10.1021/acs.orglett.4c04498
Qi Quan, Yan Li, Zhefan Zhang, Erik V. Van der Eycken, Lingchao Cai, Liangliang Song
{"title":"Rh(III)-Catalyzed Double C–H Activation toward Peptide–Benzazepine Conjugates","authors":"Qi Quan, Yan Li, Zhefan Zhang, Erik V. Van der Eycken, Lingchao Cai, Liangliang Song","doi":"10.1021/acs.orglett.4c04498","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04498","url":null,"abstract":"We herein report the efficient synthesis of peptide–benzazepine conjugates from Lys-based peptides and acroleins via Rh(III)-catalyzed double C–H activation. This reaction features mild reaction conditions, broad scope, high atom and step economies, and excellent chemo- and site selectivity. The synthetic utility of this strategy is further demonstrated by scale-up experiments and product derivatizations, including diverse late-stage ligations based on the aldehyde moiety. The preliminary biological activity studies show that peptide–benzazepine conjugates have good antifungal activities toward crop and forest pathogenic fungi.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"291 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880135","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":"Photoredox Catalytic Defluoroalkylation of gem-Difluoroalkenes with Secondary N-Alkylanilines via C–F/C–H Coupling","authors":"Haiyang Hu, Baokai Yang, Yongcan Liu, Wengang Xu, Congjian Xia, Guoqiang Xu, Mingbo Wu","doi":"10.1021/acs.orglett.4c04432","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04432","url":null,"abstract":"To provide fluorinated allylamines, a visible-light photocatalytic C–F/C–H coupling of easily accessible <i>gem</i>-difluoroalkenes and secondary <i>N</i>-alkylanilines was described. The protocol proceeded under mild conditions, with excellent functional group compatibility and a broad scope including complex natural product derivatives, thus providing a green method for the preparation of high-value functionalized monofluoroalkenes. Mechanistic studies elucidated a photoredox catalyzed radical–radical coupling pathway.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"48 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874606","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":"Organophotoredox-Catalyzed Chemoselective Deprotection for Phenolic Ethers Driven by the Oxophilicity of Silicon","authors":"Tanumoy Mandal, Malekul Islam, Sanju Das, Aznur Azim, Suman De Sarkar","doi":"10.1021/acs.orglett.4c04357","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04357","url":null,"abstract":"An organophotocatalyzed approach for the chemoselective dealkylation of phenols is developed. This method demonstrates exceptional selectivity toward the cleavage of phenolic ethers over equivalent aliphatic ethers and alkyl benzoates, presenting a broad range of functional group sustainability. This strategy also enables selective debenzylation of phenols in the presence of reduction-sensitive functional groups. Mechanistic studies and photophysical experiments provide evidence for the selective disintegration of C–O bonds through photo-oxidation, facilitated by the oxophilicity of silicon.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"53 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874605","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 : 2024-12-21DOI: 10.1021/acs.orglett.4c03902
Aurelia Pastor, Carmen Lopez-Leonardo, Guillermo Cutillas-Font, Alberto Martinez-Cuezva, Marta Marin-Luna, Jose-Antonio Garcia-Lopez, Isabel Saura-Llamas, Mateo Alajarin
{"title":"Unveiling the Phosphine-Mediated N-Transfer from Azide to Isocyanide en Route to Carbodiimides and 4-Imino-1,3,2-diazaphosphetidines","authors":"Aurelia Pastor, Carmen Lopez-Leonardo, Guillermo Cutillas-Font, Alberto Martinez-Cuezva, Marta Marin-Luna, Jose-Antonio Garcia-Lopez, Isabel Saura-Llamas, Mateo Alajarin","doi":"10.1021/acs.orglett.4c03902","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03902","url":null,"abstract":"Intramolecular reactions between isocyano and iminophosphorane functions yield species containing an embedded 1,3,2-diazaphosphetidine ring, as result of the [2 + 2] cycloaddition of the primary reactive product, the cyclic carbodiimide, with a second unit of reactant. DFT studies reveal a first rate-determining step entailing a [2 + 1] cycloaddition involving the isocyanide carbon atom and the P═N double bond, with the further intervention of a dipolar precursor of the intermediate carbodiimide. The 1,3,2-diazaphosphetidine ring of the final products is shown to be hydrolytically and thermally labile.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"55 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867614","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":"DMAP-Catalyzed [4 + 2] Annulation of Hex-5-en-2-ynoates with Electron-Poor Alkenes","authors":"Dongqiu Li, Jiale Wu, LuLu Yang, Shuangshuang Cai, Yuhai Tang, Yang Li, Silong Xu","doi":"10.1021/acs.orglett.4c03842","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03842","url":null,"abstract":"Herein, we report a DMAP-catalyzed [4 + 2] annulation reaction of hex-5-en-2-ynoates <b>1</b> with electron-poor alkenes <b>2</b>, which affords exocyclic olefinic cyclohexenes <b>3</b> in good yields and excellent regio-, diastereo-, and <i>E</i>/<i>Z</i> selectivities. Distinguished from previous allenoate- or alkynoate-based substrates, hex-5-en-2-ynoates <b>1</b> use the β- and ε-carbons for the bond formation, presenting new and regiodivergent C<sub>4</sub> synthons for Lewis base-catalyzed annulations.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"112 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867615","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 : 2024-12-20DOI: 10.1021/acs.orglett.4c03808
Shao-Jie Cheng, Xin-Li Zhang, Zhen-Xu Yang, Ai-Hua Wang, Zhi-Shi Ye
{"title":"Palladium-Catalyzed N-Allylic Alkylation of Pyrazoles and Unactivated Vinylcyclopropanes","authors":"Shao-Jie Cheng, Xin-Li Zhang, Zhen-Xu Yang, Ai-Hua Wang, Zhi-Shi Ye","doi":"10.1021/acs.orglett.4c03808","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03808","url":null,"abstract":"An efficient palladium-catalyzed <i>N</i>-allylic alkylation of pyrazoles and unactivated vinylcyclopropanes is demonstrated, affording various <i>N</i>-alkyl pyrazoles in ≤99% yield. This protocol displays high atom economy, a broad range of substrates, and excellent regioselectivity and stereoselectivity. Late-stage modification of bioactive molecules, scaled-up reaction, and divergent derivatization documented the practicability of this methodology. The preliminary mechanistic investigation hinted that the Pd–H species promotes the ring opening of cyclopropanes.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"44 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857761","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 : 2024-12-20DOI: 10.1021/acs.orglett.4c04385
Nerea Álvarez-Llorente, Anton J. Stasyuk, Alberto Diez-Varga, Sergio Ferrero, Miquel Solà, Héctor Barbero, Celedonio M. Álvarez
{"title":"Multitopic Corannulene–Porphyrin Hosts for Fullerenes: A Three-Layer Scaffold for Precisely Designed Supramolecular Ensembles","authors":"Nerea Álvarez-Llorente, Anton J. Stasyuk, Alberto Diez-Varga, Sergio Ferrero, Miquel Solà, Héctor Barbero, Celedonio M. Álvarez","doi":"10.1021/acs.orglett.4c04385","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04385","url":null,"abstract":"A method to synthesize cofacial dimeric porphyrins bearing eight corannulene units has been developed. It relies on the stability of octahedral CO-capped Ru(II) complexes linked by N-donor ligands. This specific arrangement provides an optimal scaffold to accommodate fullerenes by imposing corannulene groups at a precise distance and relative orientation. Their capabilities for C<sub>60</sub> recognition have been thoroughly assessed, revealing that each system can encapsulate up to four guests, giving rise to a compact supramolecular van der Waals complex echoing a discrete donor–acceptor–donor trilayer offering significant potential properties for further exploitation.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"1 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857832","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}