Pub Date : 2024-12-23DOI: 10.1021/acs.orglett.4c03878
Yoshihiko Yamamoto, Yuto Ide, Takeshi Yasui
We report the dearomative transformation of pyridin-3-ols via oxidopyridinium (5 + 4) cycloaddition with o-quinodimethanes, leading to 2,3,6,7-tetrahydro-1H-2,6-methanobenzo[d]azonin-12-ones. The chemoselective derivatization of the obtained cycloadduct was also investigated to demonstrate the synthetic potential of the obtained cycloadduct.
{"title":"Dearomative Transformation of Pyridin-3-ols into 2,3,6,7-Tetrahydro-1H-2,6-methanobenzo[d]azonin-12-ones via Oxidopyridinium/o-Quinodimethane (5 + 4) Cycloaddition","authors":"Yoshihiko Yamamoto, Yuto Ide, Takeshi Yasui","doi":"10.1021/acs.orglett.4c03878","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03878","url":null,"abstract":"We report the dearomative transformation of pyridin-3-ols via oxidopyridinium (5 + 4) cycloaddition with <i>o</i>-quinodimethanes, leading to 2,3,6,7-tetrahydro-1<i>H</i>-2,6-methanobenzo[<i>d</i>]azonin-12-ones. The chemoselective derivatization of the obtained cycloadduct was also investigated to demonstrate the synthetic potential of the obtained cycloadduct.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"32 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880170","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}
We have developed a glycosyl radical-based synthesis of C-alkyl glycosides through a deoxygenative Giese addition–reduction–cyclization cascade, in which readily available 1-hydroxy carbohydrates serve as precursors for glycosyl radicals and aryl alkenes function as radical acceptors. This reaction not only provides an effective method for accessing a previously underexplored class of functionalized cyclopropanes but also enhances the application of Giese addition in the synthesis of C-alkyl glycosides by derivatizing the radical intermediate generated through polar cyclization to yield a cyclopropane.
{"title":"Glycosyl Radical-Based Synthesis of C-Alkyl Glycosides Bearing a Cyclopropane via a Deoxygenative Giese Addition–Reduction–Cyclization Cascade","authors":"Jian-Yu Pang, Li-Min Feng, Wen-Feng Zhang, De-Yong Liu, Jing Wang, Ruo-Han Wei, Xiang-Guo Hu","doi":"10.1021/acs.orglett.4c04510","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04510","url":null,"abstract":"We have developed a glycosyl radical-based synthesis of <i>C</i>-alkyl glycosides through a deoxygenative Giese addition–reduction–cyclization cascade, in which readily available 1-hydroxy carbohydrates serve as precursors for glycosyl radicals and aryl alkenes function as radical acceptors. This reaction not only provides an effective method for accessing a previously underexplored class of functionalized cyclopropanes but also enhances the application of Giese addition in the synthesis of <i>C</i>-alkyl glycosides by derivatizing the radical intermediate generated through polar cyclization to yield a cyclopropane.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"77 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874604","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 : 2024-12-23DOI: 10.1021/acs.orglett.4c04222
Feng Zhang, Xiu-Fen Cheng, Xiaolin Liang, Duo-Duo Hu, Qian Gao, Hongliang Wang, Peng Wu, Yan Li
The structure of the novel photoactive nickel species was simulated by density functional theory (DFT)/time-dependent density functional theory (TD-DFT) calculations. The application of the simplified photoactive nickel catalyst was demonstrated in a photoinduced nickel-catalyzed three-component arylsulfonation of 1,6-enynes. This reaction was autopromoted and proceeded in the absence of an additional photocatalyst. This methodology exhibited mild conditions, a broad substrate scope, and high efficiency.
{"title":"Photoinduced Autopromoted Ni-Catalyzed Three-Component Arylsulfonation Inspired by Density Functional Theory/Time-Dependent Density Functional Theory-Simulated Photoactive Nickel Species","authors":"Feng Zhang, Xiu-Fen Cheng, Xiaolin Liang, Duo-Duo Hu, Qian Gao, Hongliang Wang, Peng Wu, Yan Li","doi":"10.1021/acs.orglett.4c04222","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04222","url":null,"abstract":"The structure of the novel photoactive nickel species was simulated by density functional theory (DFT)/time-dependent density functional theory (TD-DFT) calculations. The application of the simplified photoactive nickel catalyst was demonstrated in a photoinduced nickel-catalyzed three-component arylsulfonation of 1,6-enynes. This reaction was autopromoted and proceeded in the absence of an additional photocatalyst. This methodology exhibited mild conditions, a broad substrate scope, and high efficiency.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"83 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880241","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}
We present a tandem aza-Heck/Suzuki cross-coupling reaction of O-phenyl hydroxamic ethers with readily available arylboronic and alkenyl boronic acids. This protocol is enabled by a palladium catalyst paired with chiral phosphoramidite ligands, particularly under mild reaction conditions, yielding efficient and succinct synthetic routes to chiral isoindolinones with high enantioselectivity. Furthermore, this reaction exhibits excellent functional group compatibility and a rich diversity of subsequent transformations.
{"title":"Enantioselective Synthesis of Isoindolinone by Sequential Palladium-Catalyzed Aza-Heck/Suzuki Coupling Reaction","authors":"Lei Wang, Wenyu Zhang, Shuaijie Wu, Qing Wu, Ying Han, Chao-Guo Yan, Guodong Zhang","doi":"10.1021/acs.orglett.4c04239","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04239","url":null,"abstract":"We present a tandem aza-Heck/Suzuki cross-coupling reaction of <i>O</i>-phenyl hydroxamic ethers with readily available arylboronic and alkenyl boronic acids. This protocol is enabled by a palladium catalyst paired with chiral phosphoramidite ligands, particularly under mild reaction conditions, yielding efficient and succinct synthetic routes to chiral isoindolinones with high enantioselectivity. Furthermore, this reaction exhibits excellent functional group compatibility and a rich diversity of subsequent transformations.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"85 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874250","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 : 2024-12-23DOI: 10.1021/acs.orglett.4c04500
Xiaolong Wang, Yan Fu, Zhenshan Guo, Aijun Lin, Qingzhong Jia, Chunhua Han
We report herein an efficient and site-selective electrophilic trifluoromethylthiolation of indolines. In the absence of any catalyst or additive, C5-selective trifluoromethylthiolation could proceed at room temperature. With palladium used as the catalyst, the selectivity was reversed completely, giving C7-selecive trifluoromethylthiolated products. This reaction features good functional group tolerance, simple operation, mild conditions, and scale-up application. The potential utilities of the products were shown by further transformations.
{"title":"Site-Selective Electrophilic Trifluoromethylthiolation for the Synthesis of C5- or C7-SCF3-Substituted Indolines","authors":"Xiaolong Wang, Yan Fu, Zhenshan Guo, Aijun Lin, Qingzhong Jia, Chunhua Han","doi":"10.1021/acs.orglett.4c04500","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04500","url":null,"abstract":"We report herein an efficient and site-selective electrophilic trifluoromethylthiolation of indolines. In the absence of any catalyst or additive, C5-selective trifluoromethylthiolation could proceed at room temperature. With palladium used as the catalyst, the selectivity was reversed completely, giving C7-selecive trifluoromethylthiolated products. This reaction features good functional group tolerance, simple operation, mild conditions, and scale-up application. The potential utilities of the products were shown by further transformations.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"24 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874516","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 : 2024-12-23DOI: 10.1021/acs.orglett.4c04105
Yinqiao Wang, Wenlong Tong, Jiaxi Xu
Various 4-vinyl-1,2-oxaphospholane 2-oxides are prepared in good to excellent yields from vinyloxiranes and in situ-generated phosphenes from phosphoryl diazomethanes via the phosphene-induced ring expansion of oxiranes. The reaction is a novel and expeditious strategy for the synthesis of 1,2-oxaphospholane 2-oxide derivatives, featuring ring expansion of readily available starting materials, high atom economy, no catalyst, a fast reaction rate, broad functional group tolerance, high yields, and separable diastereomers.
{"title":"Construction of 4-Vinyl-1,2-oxaphospholane 2-Oxides from Vinyloxiranes and Phosphoryl Diazomethanes","authors":"Yinqiao Wang, Wenlong Tong, Jiaxi Xu","doi":"10.1021/acs.orglett.4c04105","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04105","url":null,"abstract":"Various 4-vinyl-1,2-oxaphospholane 2-oxides are prepared in good to excellent yields from vinyloxiranes and in situ-generated phosphenes from phosphoryl diazomethanes via the phosphene-induced ring expansion of oxiranes. The reaction is a novel and expeditious strategy for the synthesis of 1,2-oxaphospholane 2-oxide derivatives, featuring ring expansion of readily available starting materials, high atom economy, no catalyst, a fast reaction rate, broad functional group tolerance, high yields, and separable diastereomers.","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":"142880126","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 : 2024-12-23DOI: 10.1021/acs.orglett.4c04495
Ivan Borkovic, Zorana Ferjancic, Filip Bihelovic
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.
{"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}
Pub 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
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.
{"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}
Pub 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
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.
{"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}
Pub Date : 2024-12-23DOI: 10.1021/acs.orglett.4c04498
Qi Quan, Yan Li, Zhefan Zhang, Erik V. Van der Eycken, Lingchao Cai, Liangliang Song
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.
{"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}
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