可见光促进喹喔啉-2(1H)-酮的苯甲酰化反应  

Visible light promoted benzoylation of quinoxalinone-2(1H)-ones

作　　者：周冰洁 陈景超[1] 李泓江 保德玉 孟云艳 邓耀 孙蔚青 樊保敏[1,2] Binjie Zhou;Jingchao Chen;Hongjiang Li;Deyu Bao;Yunyan Meng;Yao Deng;Weiqing Sun;Baomin Fan(Key Laboratory of Chemistry in Ethnic Medicinal Resources,State Ethnic Affairs Commission&Ministry of Education,Yunnan Minzu University,Kunming 650500,China;School of Chemistry and Environment,Yunnan Minzu University,Kunming 650500,China)

机构地区：[1]云南民族大学,民族药资源化学国家民族事务委员会-教育部重点实验室,昆明650500 [2]云南民族大学化学与环境学院,昆明650500

出　　处：《科学通报》2023年第21期2805-2811,共7页Chinese Science Bulletin

基　　金：国家自然科学基金(21961045,22061048)资助。

摘　　要：喹喔啉酮C-3官能团化衍生物常具有突出的生物活性,虽然人们已经成功利用过渡金属和强氧化剂催化手段获得此类化合物,但是这些反应的条件相对苛刻.为了发展符合“绿色化学”理念的合成方法,其他环境友好和原子转化率高的制备方法,光催化和电催化合成策略在喹喔啉酮C-3官能团化的应用也相继被开发出来,成功得到了一系列芳基化、烷基化、胺化、磷酰化、磺化和酰化的3-取代喹喔啉-2(1H)-酮衍生物.鉴于3-酰基喹喔啉-2(1H)-酮类化合物表现出的特殊生物活性,本文将苯甲酰氯作为酰基自由基源,利用可见光催化手段,成功实现了苯甲酰氯对喹喔啉-2(1H)-酮的C-3酰基化反应,并提出了反应可能的机理.Quinoxalinone-2(1H)-ones is an important class of benzodiazine heterocyclic compounds.Many quinoxalinone derivatives exhibit good biological activities,such as anticoagulant,antitumor,and can serve as pteridine reductase inhibitors.3-Acylquinoxaline-2(1H)-ones are a special class of pharmacophores in the field of medicinal chemistry and have received considerable attention.In general,the synthetic methods for 3-acylquinoxaline-2(1H)-ones are divided into two categories.The traditional oxidation methods include direct oxidation of benzyl quinoxaline,Kornblum oxidation and the oxidation ring contraction of benzodiazepines.This type of oxidation reaction requires the preparation of the corresponding benzylation products of quinoxalinones in advance,and they are associated with less functional groups tolerance under the strong oxidation conditions.The second method for the synthesis of 3-acylquinoxaline-2(1H)-ones is the radical reactions between α-keto acids and benzaldehyde as acyl radical sources to synthesize 3-acylquinoxaline-2(1H)-ones.Besides,α-keto acids and aldehydes have also been employed as radical sources in the preparation of 3-acylquinoxaline-2(1H)-ones.Aryl chlorides are widely used as important raw material in the field of organic synthesis because of its low price,easily accessible and high reactivity.Therefore,aryl chlorides are often regarded as a simple,direct and efficient aryl radical source.In recent years,our group has been committed to the development of visible light promoted green synthesis reactions.Due to the special biological activity of 3-acylquinoxaline-2(1H)-ketones and its great potential in drug development,we herein report our studies on the visible light promoted benzoylation of quinoxalin-2(1H)-ones.The reaction conditions were studied by using 1-benzylquinoxaline-2(1H)-one and benzoyl chloride as reaction substrates under the irradiation with blue light.Screening of various photocatalysts revealed that fac-Ir(ppy)3was the most effective photocatalyst and furnished the acylat

关 键 词：喹喔啉-2(1H)-酮 光催化反应 苯甲酰氯 苯甲酰化 

分 类 号：O626[理学—有机化学]