Tao Qinyue, Zhang Haoxiang, Ye Runyou, Zhang Yanqiong, Long Yang, Zhou Xiangge
College of Chemistry, Sichuan University, 29 Wangjiang Road, Chengdu 610064, P. R. China.
School of Pharmacy, North Sichuan Medical College, 55 Dongshun Road, Nanchong 637000, P. R. China.
J Org Chem. 2024 Sep 20;89(18):13208-13214. doi: 10.1021/acs.joc.4c01332. Epub 2024 Aug 30.
Herein, a palladium-catalyzed 1,3-alkynyl migration of allylic alcohol for the synthesis of β-alkynyl ketone was described. This intramolecular rearrangement reaction demonstrated an enhanced reactivity compared to the traditional intermolecular alkynylation by circumventing the dimerization of alkynes, exhibiting a specific selectivity toward β-alkynyl elimination. Moreover, this reaction featured wide substrate scope, good functional group tolerance, and 100% atom economy.
本文描述了一种钯催化的烯丙醇1,3-炔基迁移反应，用于合成β-炔基酮。与传统的分子间炔基化反应相比，这种分子内重排反应通过避免炔烃的二聚化表现出更高的反应活性，对β-炔基消除具有特定的选择性。此外，该反应具有广泛的底物范围、良好的官能团耐受性和100%的原子经济性。
