{"title":"利用π-烯丙基-钯偶极子的反式保留俘获模合成平面手性环壬烯","authors":"Zheng-Xin Zhou, Yue-Liu-Ting Fu, Chen Zhang, Yuan-Heng Li, Bin-Jun Zhang, Yu-Qing Xiao, Yu-Jie Li, Li-Yan Chen, Li Rao, Ying Tan, Wen-Jing Xiao, Liang-Qiu Lu","doi":"10.1021/jacs.4c12892","DOIUrl":null,"url":null,"abstract":"<i>Trans</i>-cycloalkenes are abundant in bioactive natural products and have been used as powerful tools in chemical biology and drug discovery. However, strategies for the modular synthesis of <i>trans</i>-cycloalkenes, especially planar-chiral medium-sized ones, with high efficiency and selectivity, still remain elusive. Herein, we report a Pd-catalyzed asymmetric [7 + 2] cyclization strategy to address this challenge. As a result, two types of planar-chiral <i>trans</i>-cyclononenes bearing all-carbon chiral quaternary stereocenters are produced in up to 85% yield, >99% ee, and >19:1 dr (42 examples). The key to this success is the maintenance of the <i>trans</i>-2H configuration of the π-allyl-Pd species along with unusual linear selectivity during the H-bond-assisted cyclization process. In addition, the conversion of planar chirality to central chirality and its application in selective bioimaging of cancer cells via a bioorthogonal reaction were performed to demonstrate the synthetic value of this methodology.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"5 1","pages":""},"PeriodicalIF":14.4000,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Modular Synthesis of Planar-Chiral Cyclononenes via trans-Retentive Trapping of π-Allyl-Pd Dipoles\",\"authors\":\"Zheng-Xin Zhou, Yue-Liu-Ting Fu, Chen Zhang, Yuan-Heng Li, Bin-Jun Zhang, Yu-Qing Xiao, Yu-Jie Li, Li-Yan Chen, Li Rao, Ying Tan, Wen-Jing Xiao, Liang-Qiu Lu\",\"doi\":\"10.1021/jacs.4c12892\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<i>Trans</i>-cycloalkenes are abundant in bioactive natural products and have been used as powerful tools in chemical biology and drug discovery. However, strategies for the modular synthesis of <i>trans</i>-cycloalkenes, especially planar-chiral medium-sized ones, with high efficiency and selectivity, still remain elusive. Herein, we report a Pd-catalyzed asymmetric [7 + 2] cyclization strategy to address this challenge. As a result, two types of planar-chiral <i>trans</i>-cyclononenes bearing all-carbon chiral quaternary stereocenters are produced in up to 85% yield, >99% ee, and >19:1 dr (42 examples). The key to this success is the maintenance of the <i>trans</i>-2H configuration of the π-allyl-Pd species along with unusual linear selectivity during the H-bond-assisted cyclization process. In addition, the conversion of planar chirality to central chirality and its application in selective bioimaging of cancer cells via a bioorthogonal reaction were performed to demonstrate the synthetic value of this methodology.\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\"5 1\",\"pages\":\"\"},\"PeriodicalIF\":14.4000,\"publicationDate\":\"2025-01-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/jacs.4c12892\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c12892","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Modular Synthesis of Planar-Chiral Cyclononenes via trans-Retentive Trapping of π-Allyl-Pd Dipoles
Trans-cycloalkenes are abundant in bioactive natural products and have been used as powerful tools in chemical biology and drug discovery. However, strategies for the modular synthesis of trans-cycloalkenes, especially planar-chiral medium-sized ones, with high efficiency and selectivity, still remain elusive. Herein, we report a Pd-catalyzed asymmetric [7 + 2] cyclization strategy to address this challenge. As a result, two types of planar-chiral trans-cyclononenes bearing all-carbon chiral quaternary stereocenters are produced in up to 85% yield, >99% ee, and >19:1 dr (42 examples). The key to this success is the maintenance of the trans-2H configuration of the π-allyl-Pd species along with unusual linear selectivity during the H-bond-assisted cyclization process. In addition, the conversion of planar chirality to central chirality and its application in selective bioimaging of cancer cells via a bioorthogonal reaction were performed to demonstrate the synthetic value of this methodology.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.