Chinese Journal of Applied Chemistry ›› 2018, Vol. 35 ›› Issue (2): 181-188.DOI: 10.11944/j.issn.1000-0518.2018.02.170099

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Visible-Light-Induced Dearomatizing Spirocyclization of Alkenes Toward Perfluorinated Azaspirocyclic Cyclohexadienones

YUAN Li,LI Zengzeng,JIANG Shengming,ZHU Yong,LEI Qian,XIA Lülu,LI Lan,YU Jian,ZHANG Juan,TANG Shi()   

  1. College of Chemistry and Chemical Engineering,Engineering Laboratory for Analyse and Drugs Development of Ethnomedicine in Wuling Mountains,Jishou University,Jishou,Hu'nan 416000,China
  • Received:2017-04-01 Accepted:2017-05-18 Published:2018-02-01 Online:2018-01-29
  • Contact: TANG Shi
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.21462017, No.21662013), the Research Innovation Program for Graduates in Hu'nan province(No.16A171)

Abstract:

A visible-light-induced dearomation cyclilation of N-benzylmethacrylamides with nonafluorinated alkyl bromides or iodides toward nonafluorinated azaspirocyclic cyclo-hexadienones was developed. Under the irradiation of blue light-emitting diode(LED) light, using fac-Ir(ppy)3(fac=facial, ppy=2-phenylpyridyl) as the photocatalyst, N-benzylmethacrylamides and nonafluorinated alkyl bromides or iodides underwent cascade dearomation/cyclilation under optimal conditions, leading to a series of perfluorinating azaspirocyclic cyclohexadienones in 61%85% yield, as well as introducing a series of perfluorinated moieties including CF3, C3F7, C4F9, C6F13, C8F17, CH2CF2, CF2CO2Et(Et:Ethyl). Given the broad substrate scope, mild reaction conditions and green catalytic systems, this protocol provides a green, effective and quick approach to pharmaceutically important cyclohexadienones.

Key words: perfluorinated, dearomative cyclilation, visible-light-induced, azaspirocyclic cyclohexadienones