Selectivity for Alkynyl or Allenyl Imidamides and Imidates in Copper-Catalyzed Reactions of Terminal 1,3-Diynes and Azides
Selectivity for Alkynyl or Allenyl Imidamides and Imidates in Copper-Catalyzed Reactions of Terminal 1,3-Diynes and Azides
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DOI：
10.1021/acs.orglett.0c03861
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发表时间：
2021-01-14
期刊：
影响因子：
5.2
通讯作者：
Lee, Daesung
中科院分区：
文献类型：
--
作者：
Ghorai, Sourav;Lee, Daesung
描述了铜催化的末端1，3-二炔与缺电子叠氮化物的反应，以生成3-炔基或2，3-二烯基亚胺酰胺和亚胺酯。选择性取决于二炔取代基和亲核试剂，其与从相应的三唑前体产生的烯酮亚胺中间体反应。含炔丙基乙酸酯的1，3-二炔反应生成[3]-cumulenyl imidamides，而使用甲醇作为捕获剂的反应选择性地生成2，3-二烯基imidates。五元杂环是由含有高炔丙基羟基或胺取代基的1，3-二炔得到的。
Copper-catalyzed reactions of terminal 1,3-diynes with electron-deficient azides to generate either 3-alkynyl or 2,3-dienyl imidamides and imidates are described. The selectivity depends on the diyne substituents and the nucleophile that reacts with the ketenimide intermediate generated from the corresponding triazole precursor. Reactions of 1,3-diynes containing a propargylic acetate afford [3]cumulenyl imidamides, while reactions using methanol as the trapping agent selectively generate 2,3-dienyl imidates. Five-membered heterocycles were obtained from 1,3-diynes containing a homopropargylic hydroxyl or amine substituent.