铜催化对亚甲基苯醌/偶氮试剂/水三组分反应合成苯并呋喃-2-酮类化合物

doi:10.11944/j.issn.1000-0518.2019.11.190078

摘要/Abstract

摘要：

发展了一种高效、简便的潜在生物活性的含氰苯并呋喃-2-酮类化合物的合成新方法。以廉价碘化亚酮为催化剂,锌粉为添加剂,催化对亚甲基苯醌与1,1-偶氮双(环己烷甲腈)和H₂O三组分反应,经历1,6-共轭加成/芳构化,惰性碳-碳键断裂,以及后续的串联自由基插氰/环化及水解等步骤,“一锅法”快速合成了一系列含氰苯并呋喃酮结构的化合物。为含氰苯并呋喃酮类化合物的合成提供一条简便而高效的途径,同时也为对亚甲基苯醌类化合物的高值化应用提供一个新的思路。

关键词: C—C键官能化, 1,1-偶氮双(环己烷甲腈), 铜催化, 苯并呋喃酮, 对亚甲基苯醌

Abstract:

A new and efficient method for the synthesis of potentially biologically active cyano-containing benzofuran-2-one derivatives has been developed. In the presence of low-cost CuI and zinc powder, the three-component reactions of para-quinone methides with 1,1-azobis(cyclohexanecarbonitrile) and H₂O proceed smoothly through radical cascades, including 1,6-conjugate addition/aromatization, inert C(aryl)—C(t-butyl) bond cleavage and downstream cyano-insertion/cyclization/hydrolysis, which leads to a series of cyano-containing benzofuran-2-ones. This method offers a simple and efficient way for the synthesis of cyano-containing benzofuranone derivatives, as well as a new idea for the high-value application of para-quinone methides.

Key words: C—C bond functionalization, 1,1'-azobis(cyanocyclohexane), copper catalysis, benzofuranone, para-quinone methides

盛回香,余健,王硕文,徐振华,唐石. 铜催化对亚甲基苯醌/偶氮试剂/水三组分反应合成苯并呋喃-2-酮类化合物[J]. 应用化学, 2019, 36(11): 1266-1274.

SHENG Huixiang,YU Jian,WANG Shuowen,XU Zhenhua,TANG Shi. Copper-Catalyzed Three-Component Synthesis of Benzofuran-2-one from para-Quinone Methides/Azo Reagent/H₂O[J]. Chinese Journal of Applied Chemistry, 2019, 36(11): 1266-1274.

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