有机催化邻羟基官能化的对甲亚基苯醌和β-氧代酰基吡唑的不对称[4+2]环化合成光学活性3,4-二氢香豆素衍生物  

Optically Active 3,4-Dihydrocoumarins via Organocatalyzed Asymmetric[4+2]Annulation of ortho-Hydroxyl Functionalized p-Quinone Methides withβ-Keto Acylpyrazoles

作　　者：赵敏 李霏 程益政 王有名[1] 周正洪[1] Zhao Min;Li Fei;Cheng Yizheng;Wang Youming;Zhou Zhenghong(Institute and State Key Laboratory of Elemento-organic Chemistry,College of Chemistry,Nankai University,Tianjin 300071;Department of Chemistry,College of Chemistry,Nankai University,Tianjin 300071)

机构地区：[1]南开大学化学学院元素有机化学国家重点实验室,天津300071 [2]南开大学化学学院化学系,天津300071

出　　处：《有机化学》2021年第10期4039-4049,共11页Chinese Journal of Organic Chemistry

摘　　要：发展了一种有机催化的邻羟基苯基取代对甲亚基苯醌和β-氧代酰基吡唑之间的不对称[4+2]环化反应,为光学活性3,4-二氢香豆素衍生物的获取提供了有效途径.在衍生自奎宁的手性双功能方酰胺催化下,一系列邻羟基苯基取代对甲亚基苯醌和β-氧代酰基吡唑可以在温和的条件下顺利地发生反应,以高产率和优秀的非对映及对映选择性得到相应的多取代3,4-二氢香豆素衍生物.An organocatalyzed asymmetric formal[4+2]annulation of ortho-hydroxyl functionalized p-quinone methides withβ-keto acylpyrazoles has been developed,which provides an efficient approach to access optically active 3,4-dihydrocoumarins.Under the catalysis of a quinine-derived bifunctional squramide,the reactions of a wide range of ortho-hydroxyphenyl substituted p-quinone methides andβ-keto acylpyrazoles took place smoothly to generate the corresponding polysubstituted 3,4-dihydrocoumarins in good yields with high levels of diastereo-and enantio-selectivities(up to 96%yield,>19/1 dr and 98%ee)under mild reaction conditions.

关 键 词：不对称合成 3 4-二氢香豆素 邻羟基苯基取代对甲亚基苯醌 β-氧代酰基吡唑 有机催化 

分 类 号：O621.251[理学—有机化学]