School of Biotechnology and Health Sciences, Wuyi University, Jiangmen, 529090, Guangdong Province, P. R. China.
Key Lab of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510641, P. R. China.
Chemistry. 2023 May 8;29(26):e202300068. doi: 10.1002/chem.202300068. Epub 2023 Mar 22.
Herein, the Pd -catalyzed construction of functionalized dihaloalkenynes from haloalkynes via a self-haloalkynylation reaction, without specialized ligands or oxidizing additives, is reported. The method tolerates a diverse range of haloalkynes, including electron-donating and electron-withdrawing functional groups, such as macrocyclic alkynols, spiro-oxy ring alkynols, and even carbazole-containing, pyrrolidine-2,5-dione-containing and silyl-protected bromoalkynes. Using an opposite lithium halide (LiX) to the haloalkyne starting material, remarkably high regio- and stereoselectivity of the haloalkynylation reaction is possible, yielding 1-bromo-2-chloroalkenyne or 2-bromo-1-chloroalkenyne products as desired.
本文报道了钯催化的通过自卤代炔基化反应从卤代炔烃构建官能化二卤代烯炔的方法，无需专门的配体或氧化添加剂。该方法可耐受多种卤代炔烃，包括供电子和吸电子官能团，如大环炔醇、螺-氧环炔醇，甚至含咔唑、吡咯烷-2,5-二酮和硅基保护的溴代炔烃。使用与卤代炔烃起始原料相反的卤化锂（LiX），卤代炔基化反应具有显著的区域和立体选择性，可以得到所需的 1-溴-2-氯烯炔或 2-溴-1-氯烯炔产物。
