BF3•Et2O促进的环丙烯基甲醇衍生物重排反应研究
收稿日期: 2024-05-13
修回日期: 2024-07-17
网络出版日期: 2024-08-19
基金资助
山东省自然科学基金(ZR2023MB043); 国家自然科学基金(22371266)
Study of BF3•Et2O-Promoted Rearrangement of Cyclopropenylcarbinols
Received date: 2024-05-13
Revised date: 2024-07-17
Online published: 2024-08-19
Supported by
Natural Science Foundation of Shandong Province(ZR2023MB043); National Natural Science Foundation of China(22371266)
γ-亚乙烯基-丁烯酸内酯和苯并富烯结构单元在活性天然产物和药物化学中都具有重要的意义. 环丙烯基甲醇衍生物在BF3•Et2O的促进下, 脱除羟基后诱导环丙烯C—C断键反应的发生, 并形成联烯碳正离子中间体, 最后经不同的异构重排路径可以“一锅”实现γ-亚乙烯基-丁烯酸内酯和苯并富烯两类化合物的构建. 该合成方法拓展了两类化合物的合成策略, 二者的总收率可达68%~99%, 探究还发现电子效应和反应温度对二者的比例有着较大影响. 此外, 该反应为环丙烯结构的精准C—C键断裂提供了新方法.
关键词： 环丙烯; BF3•Et2O; γ-亚乙烯基-丁烯酸内酯; 苯并富烯; 碳−碳键断裂
荀苗苗 , 郭晶晶 , 马文兵 , 李宇强 , 袁长春 , 傅凯 . BF3•Et2O促进的环丙烯基甲醇衍生物重排反应研究[J]. 有机化学, 2024 , 44(9) : 2760 -2776 . DOI: 10.6023/cjoc202405015
γ-Ylidenebutenolides and benzofulvenes are of considerable importance in natural product and medicinal chemistry. Cyclopropenylcarbinols were promoted by BF3•Et2O to induce the C—C bond cleavage reaction of cyclopropenes via dehydroxylation to form an allene carbocation intermediate. This leads to the construction of γ-ylidenebutenolide and benzofulvene compounds in one pot via different isomerization rearrangement paths. This synthetic strategy expands the synthesis methods of two types of compounds, achieving a total yield of 68%~99%. In addition, the electronic effect and reaction temperature considerably influence the ratio of the two compounds. Moreover, the reaction provides a new method for precise C—C bond cleavage of cyclopropenes.
Key words： cyclopropene; BF3•Et2O; γ-alkylidenebutenolide; benzofulvene; C—C bond cleavage
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