Tandem asymmetric dearomatized functionalization reaction of phenols with Evans-ynamides enabled by divergent electrophiles  

作　　者：Ying-Qi Zhang Gan-Lu Qian Yun Liu Jia-Hui Li Xin Hong Zhou Xu Bo Zhou Long-Wu Ye 

机构地区：[1]State Key Laboratory of Physical Chemistry of Solid Surfaces,Key Laboratory of Chemical Biology of Fujian Province,and College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China [2]Center of Chemistry for Frontier Technologies,Department of Chemistry,State Key Laboratory of Clean Energy Utilization,Zhejiang University,Hangzhou 310027,China [3]Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy,School of Pharmacy,Xuzhou Medical University,Xuzhou 221004,China [4]State Key Laboratory of Elemento-Organic Chemistry,Nankai University,Tianjin 300071,China [5]State Key Laboratory of Organometallic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China

出　　处：《Science China Chemistry》2025年第2期649-660,共12页中国科学(化学英文版)

基　　金：supported by the National Natural Science Foundation of China(22125108 and 22121001 for Ye LW,22122109 and 22271253 for Hong X);the National Key R&D Program of China(2022YFA1504301,Hong X);the Zhejiang Provincial Natural Science Foundation of China(LDQ23B020002,Hong X);the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(SNZJU-SIAS-006,Hong X);the Beijing National Laboratory for Molecular Sciences(BNLMS202102,Hong X);the CAS Youth Interdisciplinary Team(JCTD-2021-11,Hong X);the Fundamental Research Funds for the Central Universities(226-2022-00140,226-2022-00224,and 226-2023-00115,Hong X);the State Key Laboratory of Physical Chemistry of Solid Surfaces(202210,Hong X);the Leading Innovation Team grant from the Department of Science and Technology of Zhejiang Province(2022R01005,Hong X);the Natural Science Foundation of Jiangsu Province(BK20211059);National Found for Fostering Talents of Basic Science(NFFTBS,J1310024).

摘　　要：Herein,we disclose a highly regio-/chemoselective tandem asymmetric dearomatized halofunctionalization reaction of phenoltethered ynamides with diverse electrophilic halogenation sources in a catalyst-free manner for the practical and rapid assembly of a series of halogenated spirocyclic enones.Besides,the related dearomatized selenation and protonation are also achieved,affording the corresponding selenated and protonated spirocycles in high efficiency.Moreover,the enantioselectivities of these products can be perfectly induced by Evans auxiliaries(99%ees).Significantly,this protocol not only represents the first tandem asymmetric halofunctionalization reaction of phenol derivatives,but also constitutes the first asymmetric halogenation/selenation of ynamides.Theoretical calculations indicate a remote induction model of Evans chiral auxiliary-attached keteniminium.

关 键 词：ALKYNES cyclization DEAROMATIZATION Evans chiral auxiliary SPIROCYCLES 

分 类 号：O621.25[理学—有机化学]