Brönsted酸性离子液体催化α-羟基丙酮和2-苯基吲哚反应合成苯并[a]咔唑

doi:10.1016/S1872-2067(19)63370-X

催化学报 ›› 2019, Vol. 40 ›› Issue (8): 1135-1140.DOI: 10.1016/S1872-2067(19)63370-X

Brönsted酸性离子液体催化α-羟基丙酮和2-苯基吲哚反应合成苯并[a]咔唑

李明浩^a, 吴丰田^a, 顾彦龙^a,b

a 华中科技大学化学与化工学院, 能量转换与存储材料化学教育部重点实验室, 材料化学与服役失效湖北省重点实验室, 湖北武汉 430074;
b 中国科学院兰州化学与物理研究所羰基合成与选择氧化国家重点实验室, 甘肃兰州 730000

收稿日期:2019-03-13 修回日期:2019-04-03 出版日期:2019-08-18 发布日期:2019-06-21
通讯作者: 顾彦龙
基金资助:
国家自然科学基金（21761132014，21872060）；中央高校基本科研业务费专项资金（2016YXZD033，2019kfyXJJS072）；材料化学与服役失效湖北省重点实验室开放基金（2017MCF01K）.

Brönsted acidic ionic liquid catalyzed synthesis of benzo[a]carbazole from renewable acetol and 2-phenylindoles in a biphasic system

Minghao Li^a, Fengtian Wu^a, Yanlong Gu^a,b

a Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China;
b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China

Received:2019-03-13 Revised:2019-04-03 Online:2019-08-18 Published:2019-06-21
Supported by:
This work was supported by the National Natural Science Foundation of China (21761132014, 21872060), the Fundamental Research Funds for the Central Universities of China (2016YXZD033), the Fundamental Research Funds for the Central Universities (2019kfyXJJS072), and Opening fund of Hubei Key Laboratory of Material Chemistry and Service Failure (2017MCF01K).

摘要/Abstract

摘要： 以生物质基平台化合物为原料合成含氧/氮杂环是实现生物质高值转化的重要途径.α-羟基丙酮可通过生物质分段热解获得，是一种重要的生物质平台化合物.尽管吡嗪，恶唑啉，呋喃，和喹喔啉等α-羟基丙酮衍生化杂环化合物已有报道，但将α-羟基丙酮转化为其它类型杂环仍具有很大的吸引力.
苯并[a]咔唑化合物因其在医药和光学材料有广泛的应用而备受关注.在过去二十年里，开发出了许多合成苯并[a]咔唑的方法，其中从简单易得的2-苯基吲哚出发，构建苯并[a]咔唑的方法最具吸引力，但目前基于2-苯基吲哚合成苯并[a]咔唑的报道只有4例：（1）ln（OTf）₃催化2-苯基吲哚和炔丙基醚的[4+2]反应；（2）Pd催化2-苯基吲哚与端炔氧化环化；（3）Rh（Ⅲ）催化2-苯基吲哚与α-重氮羰基化合物串联环化；（4）BiCl₃催化2-苯基吲哚与α-溴乙缩醛苯环化反应.考虑到苯并[a]咔唑化合物广泛的应用性，从简单易得的原料出发，发展新型的（例如非过渡金属催化）构建该类杂环的方法十分有必要.
本文报道了Brönsted酸性离子液体催化2-苯基吲哚和生物质基α-羟基丙酮的串联反应，构建了一系列苯并[a]咔唑化合物.首先通过对催化剂、溶剂和温度等参数的筛选，确定了最佳反应条件为1a（0.3mmol），2a（0.45mmol），TfOH（10 mol%），4c（2.0 equiv.），H₂O（16.0 equiv.），硝基乙烷（1.0 mL），95℃，1h.在标准条件下，给电子和拉电子基团取代的2-苯基吲哚都可以很好地参与反应，反应收率在70%-92%之间，相对富电子2-苯基吲哚，较贫的2-苯基吲哚反应活性更高，2-呋喃或噻吩吲哚也可以顺利参与反应.在考察α-羟基丙酮同系物的反应活性时发现，α-羟基苯乙酮和α-羟基乙缩醛可以很好地参与反应，但在α-羟基苯丙酮的α位引入取代基时，目标产物不能有效生成.值得说明的是，在合成的苯并[a]咔唑化合物中，3k具有抗白血病和抗肿瘤活性，另外反应中离子液体催化体系可以重复使用5次.

关键词: 苯并[a]咔唑, Brönsted酸性离子液体, α-羟基丙酮, 2-苯基吲哚, 串联反应

Abstract: An efficient metal-free strategy for the synthesis of pharmaceutically relevant benzo[a]carbazoles from the derivatives of readily available 2-phenylindole and bio-renewable acetol in an aqueous biphasic system was developed. This protocol employed a sulfone-containing Brönsted acidic ionic liquid as the catalyst, which could be used for five times without a noticeable decrease in its activity and selectivity. Various substituted 2-phenylindoles and α-hydroxyketones participated in the reaction smoothly, with water as the sole byproduct. Mechanistically, the reaction involved the conventional carbon-nucleophile-induced Heyns-type rearrangement and downstream intramolecular olefination.

Key words: Benzo[a]carbazole, Brönsted acid ionic liquid, Bio-renewable acetol, 2-Phenylindole

李明浩, 吴丰田, 顾彦龙. Brönsted酸性离子液体催化α-羟基丙酮和2-苯基吲哚反应合成苯并[a]咔唑[J]. 催化学报, 2019, 40(8): 1135-1140.

Minghao Li, Fengtian Wu, Yanlong Gu. Brönsted acidic ionic liquid catalyzed synthesis of benzo[a]carbazole from renewable acetol and 2-phenylindoles in a biphasic system[J]. Chinese Journal of Catalysis, 2019, 40(8): 1135-1140.

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Brönsted酸性离子液体催化α-羟基丙酮和2-苯基吲哚反应合成苯并[a]咔唑

Brönsted acidic ionic liquid catalyzed synthesis of benzo[a]carbazole from renewable acetol and 2-phenylindoles in a biphasic system

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