Palladium-Catalyzed Amide-Directed Hydrocarbofunctionalization of 3-Alkenamides with Alkynes
Palladium-Catalyzed Amide-Directed Hydrocarbofunctionalization of 3-Alkenamides with Alkynes
复制标题
钯催化的 3-链烯酰胺与炔烃的酰胺定向烃官能化
DOI：
10.1021/acscatal.9b04285
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发表时间：
2020-01-17
期刊：
影响因子：
12.9
通讯作者：
He, Gang
中科院分区：
文献类型：
--
作者：
Bai, Zibo;Bai, Ziqian;He, Gang
研究了钯催化的未活化烯烃与不同炔类的羧酰胺导向加氢官能化反应。利用8-氨基喹啉助剂提高了烯烃的反应活性，并通过形成有利的五元钯配体中间体来控制区域选择性。3-在邻苯基苯甲酸促进剂的存在下，带有C4-取代烯基的烯羧酰胺与各种末端炔反应，生成？-具有高产率和区域选择性的炔基化产物。3-丁烯酰胺与内炔和羧酸发生三组分偶联反应，得到乙烯基酯产物。初步的机理研究表明，分子内迁移插入炔基或乙烯基钯物种到C=C键是负责γ-选择性炔基化或烯基化的烯烃基团。
A Pd-catalyzed carboxamide-directed hydrocarbofunctionalization reaction of unactivated alkenes with different alkynes has been developed. An 8-aminoquinoline auxiliary was utilized to increase the reactivity of the alkene and control the regioselectivity via the formation of thermodynamically favored five-membered palladacycle intermediate. 3-Alkene carboxamides bearing a C4-substituted alkene group reacted with a variety of terminal alkynes in the presence of an ortho-phenyl benzoic acid promoter, yielding ?-alkynylated products with high yields and regioselectivity. 3-Butenamide underwent a three-component coupling reaction with internal alkynes and carboxylic acids to give vinyl ester products. Preliminary mechanistic studies indicate that the intramolecular migratory insertion of alkynyl or vinyl palladium species into the C=C bond is responsible for the gamma-selective alkynylation or alkenylation of the alkene group.