2026-03-05 中国科学院（CAS）
＜関連情報＞
- https://english.cas.cn/newsroom/research-news/202603/t20260306_1151836.shtml
- https://pubs.acs.org/doi/full/10.1021/jacs.5c20677
エステルの転位によって誘起されるアルケンの触媒的遠隔二ハロゲン化 Catalytic Remote Dihalogenation of Alkenes Induced by Transposition of Esters
Chang-Hui Liu,Yilitabaier Julaiti,Zhi-Yuan Ding,Yong-Zhu Hu,Hao Zheng,and Qing-An Chen
Journal of the American Chemical Society Published February 23, 2026
DOI:https://doi.org/10.1021/jacs.5c20677
Abstract
Organic halides play an indispensable role in functional molecule synthesis and pharmaceuticals, driving continuous efforts to develop efficient synthetic strategies. While direct alkene halogenation is an ideal route to halogenated products, conventional methods are typically limited to 1,2-dihalogenation. Here, we report a phosphordiamide-catalyzed strategy for remote dihalogenation of alkenes induced by transposition of esters. Without the need for preinstalled directing groups, this approach achieves 1,4-, 1,3-, and 2,3-dihalogenation of alkenes under mild and operationally simple conditions. Terminal/internal or cis/trans allylic/homoallylic esters undergo remote dihalogenation smoothly with good functional group tolerance. Preliminary mechanistic studies indicate that the catalyst cooperates with NBS and SOCl2 to form an active intermediate, which enables selective remote dihalogenation promoted by ester transposition. Moreover, the products are readily accessible via gram-scale preparations, and their diverse transformations further highlight the protocol’s potential as a versatile synthetic platform.
