Selective Quadruple C(sp3)-F Functionalization of Polyfluoroalkyl Ketones

iScience

Zhi-Liang Shen¹  Ting Xie²  Xue-Qiang Chu²  Ya-Wen Wang²  Weidong Rao³  Shuhua Li⁴  Guo-Qiang Wang⁴  Haiyan Xu⁵ 

[1] Corresponding author;Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China;Jiangsu Provincial Key Lab for the Chemistry and Utilization of Agro-Forest Biomass, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China;Key Laboratory of Mesoscopic Chemistry of Ministry of Education, Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China;School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212003, China;

关键词: Chemistry;    Organic Chemistry;    Organic Chemistry Methods;   

DOI  :  

来源: DOAJ

【 摘 要 】

Summary: The significance of organofluorine compounds has inspired the establishment of numerous methods for the functionalization of rather inert C-F bonds. Despite advances achieved in the manipulation of C(sp2)-F bonds by employing transition-metal catalysts, such as Pd, Rh, Cu, Ni, Ru, and Ir, strategies that address the paucity of effective pathways for selective activation of multiple C(sp3)-F bonds remained challenging. In this context, we present an unprecedented coupling-aromatization-cyclization reaction of polyfluorinated ketones with diverse N- and S-nucleophiles that forms regiodefined perfluoroalkylated naphtho[1,2-b]furan/benzofuran derivatives by harnessing Co-promoted distinctive quadruple C(sp3)-F bonds cleavage relay. This chemistry involving controlled and successive selective defluorination at heteronuclear centers would greatly contribute to the preparation of drug-like heterocycles as well as the late-stage elaboration of biorelevant compounds. Controlled experiments and DFT theoretical studies revealed that the combination of cheap cobalt salt with Cs2CO3 enable expeditious C-F functionalization.

【 授权许可】

Unknown