Expedient Synthesis of Dihaloalkenynes via Pd-Catalyzed Haloalkynylation Reaction

作者:Ji, Xiaoliang; Peng, Xin; Hong, Huanliang; Xu, Yanghao; Nie, Jinli; Chen, Lu; Mo, Zongwen; Li, Yibiao*; Jiang, Huanfeng*
来源:Chemistry - A European Journal, 2023, 29(26).
DOI:10.1002/chem.202300068

摘要

Herein, the Pd-II-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.

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