可见光诱导的烯炔和多氟烷基卤环化合成含氟异喹啉酮

doi:10.11944/j.issn.1000-0518.2020.04.190140

摘要/Abstract

摘要：

发展了一种可见光诱导的1,7-烯炔与全氟烷基卤串联原子转移自由基加成(ATRA)/环化合成含氟2,4-二氢异喹啉-2(1H)-酮的反应。以多氟烷基碘或溴为自由基前体,面式-三( 2-苯基吡啶)合铱(摩尔分数1%)为光敏剂,在5 W蓝光发光二极管(LED)照射下,多种苯桥联1,7-烯炔顺利发生串联(ATRA)/环化反应,以中等到优秀(62%~84%)的产率合成了一系列多氟化异喹啉酮衍生物。此合成方法反应条件温和、清洁、高效且底物适用范围广,为具有潜在药用价值的多氟化2,4-二氢异喹啉-2(1H)-酮的合成提供新的途径。

关键词: 可见光诱导, 原子转移自由基加成, 2,4-二氢异喹啉-2(1H)-酮, 多氟烷基化, 烯炔

Abstract:

Visible light-induced reaction of 1,7-enyne with perfluoroalkyl halide through a tandem atom transfer radical addition (ATRA)/cyclization sequence, synthesizing fluorinated 2,4-dihydroisoquinoline-2(1H)-one was developed. With polyfluoroalkyl iodine or bromine as the free radical precursor, fac-Ir (ppy)₃ (molar fraction 1%) as the photosensitizer, ATRA/cyclization reactions of various benzene-linked 1,7-enyne occurred successfully under 5 W blue light emitting diode (LED) irradiation. A series of polyfluorinated isoquinolone derivatives was synthesized in modorate to excellent yields (62%~84%). This highly efficient synthetic method is mild and clean, providing a new way for the synthesis of polyfluoride 2,4-dihydroisoquinoline-2(1H)-ketone with potential medicinal value.

Key words: visible light induction, atom transfer radical addition, 2,4-dihydroisoquinoline-2(1H)-one, polyfluoroalkylation, enyne

王硕文, 刘缘, 徐振华, 曾蓉, 陈义, 唐石. 可见光诱导的烯炔和多氟烷基卤环化合成含氟异喹啉酮[J]. 应用化学, 2020, 37(4): 424-432.

WANG Shuowen, LIU Yuan, XU Zhenhua, ZENG Rong, CHEN Yi, TANG Shi. Visible-Light-Induced Cyclization of 1,n-Enyne and Polyfluoroalkyl Halides Toward Halo-perfluorinated 2,4-Dihydroisoquinoline-2(1H)-one[J]. Chinese Journal of Applied Chemistry, 2020, 37(4): 424-432.

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