可见光催化喹喔啉-2(1H)-酮与醇C(sp2)-H/O-H交叉脱氢偶联反应

doi:10.1016/S1872-2067(19)63526-6

催化学报 ›› 2020, Vol. 41 ›› Issue (8): 1168-1173.DOI: 10.1016/S1872-2067(19)63526-6

可见光催化喹喔啉-2(1H)-酮与醇C(sp²)-H/O-H交叉脱氢偶联反应

谢龙勇^a, 刘艺舒^a, 丁红汝^a, 龚绍峰^a, 谭家希^c, 何军意^b, 曹忠^b, 何卫民^a

a 湖南科技学院化学学院, 湖南永州 425100;
b 长沙理工大学电力与交通材料保护实验室, 湖南长沙 410114;
c 湖南科技大学化学化工学院, 湖南湘潭 411201

收稿日期:2019-11-30 修回日期:2019-12-28 出版日期:2020-08-18 发布日期:2020-08-08
通讯作者: 何卫民
基金资助:
湖南省自然科学基金（2019JJ20008）.

C(sp²)-H/O-H cross-dehydrogenative coupling of quinoxalin-2(1H)-ones with alcohols under visible-light photoredox catalysis

Long-Yong Xie^a, Yi-Shu Liu^a, Hong-Ru Ding^a, Shao-Feng Gong^a, Jia-Xi Tan^c, Jun-Yi He^b, Zhong Cao^b, Wei-Min He^a

a Department of Chemistry, Hunan University of Science and Engineering, Yongzhou 425100, Hunan, China;
b Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, Changsha University of Science and Technology, Changsha 410114, Hunan, China;
c School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, Hunan, China

Received:2019-11-30 Revised:2019-12-28 Online:2020-08-18 Published:2020-08-08
Supported by:
This work was supported by the Hunan Provincial Natural Science Foundation of China (2019JJ20008).

摘要/Abstract

摘要： 杂环化合物和醇的C（sp²）-H/O-H交叉脱氢偶联反应为制备杂环醚类化合物提供了一种原子和步骤经济性的方法.然而，已经报道的交叉脱氢偶联反应大部分需要使用过渡金属催化剂和/或者强氧化剂，不仅产生环境问题还增加分离成本.同时，这些合成方法还存在杂环化合物和醇的C（sp²）-H/C（sp³）-H交叉脱氢偶联反应的竞争反应，降低了反应的选择性和收率.
喹喔啉-2（1H）-酮是生物活性物质和人工药物的核心骨架结构之一，合成多样性官能化的喹喔啉-2（1H）-酮备受关注.近期多种C-3官能化喹喔啉-2（1H）-酮的合成方法被报道，但是目前没有一例通过无金属无强氧化剂条件下的喹喔啉-2（1H）-酮与醇C（sp²）-H/O-H交叉脱氢偶联反应合成3-烷氧基喹喔啉-2（1H）-酮的相关工作报道.值得一提的是，利用氧气作为氧化剂的可见光催化反应符合绿色化学的要求，在最近几年中发展迅速.
本文报道了一种通过可见光催化的喹喔啉-2（1H）-酮与醇的C（sp²）-H/O-H交叉脱氢偶联反应合成3-烷氧基喹喔啉-2（1H）-酮化合物的绿色制备方法.首先通过对光催化剂、溶剂等参数的筛选，确定了最佳反应条件为喹喔啉-2（1H）-酮化合物0.3mmol，醇0.9mmol，乙腈1.5mL，Acr⁺-MesClO₄^-2 mol%，空气作为氧化剂，3W蓝光作为光源.在最佳条件下，含有供电子、吸电子取代基的喹喔啉-2（1H）-酮化合物和含有各种取代基的烷基醇都能很好地进行反应，得到36种目标化合物，产率70%~94%.另外，成功完成了克级放大实验和一锅法串联反应.机理研究证明，该反应是喹喔啉-2（1H）-酮化合物在光催化氧化作用下生成自由基正离子，醇作为亲核试剂选择性进攻自由基正离子的C3位，最后得到目标产物.

关键词: 喹喔啉-2(1H)-酮, 醇, 可见光催化, 交叉脱氢偶联反应, 无金属反应

Abstract: An efficient and practical route to various 3-alkoxylquinoxalin-2(1H)-ones through visible-light photocatalytic C(sp²)-H/O-H cross-dehydrogenation coupling of quinoxalin-2(1H)-ones and alcohols, employing ambient air as an oxidant at room temperature under metal-free conditions, was developed.

Key words: Quinoxalin-2(1H)-ones, Alcohols, Visible-light photoredox catalysis, Cross-dehydrogenative coupling, Metal free reaction

谢龙勇, 刘艺舒, 丁红汝, 龚绍峰, 谭家希, 何军意, 曹忠, 何卫民. 可见光催化喹喔啉-2(1H)-酮与醇C(sp²)-H/O-H交叉脱氢偶联反应[J]. 催化学报, 2020, 41(8): 1168-1173.

Long-Yong Xie, Yi-Shu Liu, Hong-Ru Ding, Shao-Feng Gong, Jia-Xi Tan, Jun-Yi He, Zhong Cao, Wei-Min He. C(sp²)-H/O-H cross-dehydrogenative coupling of quinoxalin-2(1H)-ones with alcohols under visible-light photoredox catalysis[J]. Chinese Journal of Catalysis, 2020, 41(8): 1168-1173.

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可见光催化喹喔啉-2(1H)-酮与醇C(sp²)-H/O-H交叉脱氢偶联反应

C(sp²)-H/O-H cross-dehydrogenative coupling of quinoxalin-2(1H)-ones with alcohols under visible-light photoredox catalysis

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