Ghorai Sourav, Lee Daesung
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607, United States.
Org Lett. 2021 Feb 5;23(3):697-701. doi: 10.1021/acs.orglett.0c03861. Epub 2021 Jan 14.
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.
描述了末端1,3 - 二炔与缺电子叠氮化物的铜催化反应，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以及与由相应三唑前体生成的烯酮亚胺中间体反应的亲核试剂。含有炔丙基乙酸酯的1,3 - 二炔的反应生成[3]累积烯基亚胺酰胺，而使用甲醇作为捕获剂的反应选择性地生成2,3 - 二烯基亚胺酯。从含有高炔丙基羟基或胺取代基的1,3 - 二炔中获得了五元杂环。
