炔烃参与的去芳构化反应构建螺环己二烯酮类化合物的研究进展  

Progress in the Construction of Spirocyclohexadienones via Alkyne-Involving Dearomatization

作　　者：刘鹏 钟富明 廖礼豪 谭伟强[1] 赵晓丹 Liu Peng;Zhong Fuming;Liao Lihao;Tan Weiqiang;Zhao Xiaodan(School of Environmental and Municipal Engineering,Qingdao University of Technology,Qingdao 266520;School of Chemistry,Sun Yat-Sen University,Guangzhou 510006)

机构地区：[1]青岛理工大学环境与市政工程学院,青岛266520 [2]中山大学化学学院,广州510006

出　　处：《有机化学》2023年第12期4019-4035,共17页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.22171292,22101304);广东特支计划科技创新领军人才(No.2019TX05Y638)资助项目.

摘　　要：螺环己二烯酮类化合物不仅广泛存在于生物活性分子中,而且是合成天然产物的关键中间体.由于其重要性,它们的高效合成引起了合成化学家的关注.特别地,在过去几年里,大量的研究报道是关于通过炔烃参与的芳基去芳构化反应构建螺环己二烯酮类化合物.这些反应的成功得益于自由基、亲电试剂或金属催化剂在光催化、电催化、化学氧化等条件下对炔烃π键进行活化,进而诱发随后的去芳构化的反应模式.对近五年来缺电子炔烃、普通炔烃、富电子炔烃参与的酚类衍生物去芳构化以实现螺环己二烯酮类衍生物的高效构建的研究进展进行系统总结,并对使用的诱发手段加以细分,最后对该领域的发展进行了展望.本文将从炔烃参与去芳构化构建螺环己二烯酮类化合物角度出发,介绍近五年来的研究进展.Spirocyclohexadienones are not only widely present in bioactive molecules,but also act as key synthetic intermediates for the synthesis of natural products.Owing to the great importance of these compounds,their efficient synthesis has drawn considerable attention from synthetic chemists.In particular,there are many reports about the synthesis of spirocyclohexadienone derivatives via alkyne-involving dearomatization in the past few years.The success of these reactions benefits from the reaction mode:the activation of alkyneπbond by radicals,electrophiles,or metal catalysts under the conditions of photocatalysis,electrocatalysis,or chemical oxidation,and then the subsequent dearomatization process.The advances in electron-deficient,electron-ordinary,and electron-rich alkynes-participated dearomatization of phenolic derivatives to realize the efficient construction of spirocyclohexadienone derivatives in recent five years are systematically summarized.During the discussion,the used triggering ways are subdivided.At last,the prospects of this field are discussed.

关 键 词：去芳构化 炔烃 螺环己二烯酮 合成方法 研究进展 

分 类 号：O621.251[理学—有机化学]