Copper-Catalyzed Yne-Allylic Substitutions Using Stabilized Nucleophiles

作者：Niu, Shengtong; Luo, Yingkun; Xu, Chao; Liu, Jinggong; Yang, Shuang; Fang, Xinqiang^*

来源：ACS Catalysis, 2022, 12(12): 6840-6850.

DOI：10.1021/acscatal.2c00911

• copper catalysis
• allylic substitution
• stabilized nucleophile
• enyne
• regioselective reaction

Using stabilized "soft" nucleophiles in coppercatalyzed allylic substitutions is highly desirable but remains an unsolved challenge for the last 40 years. In this work, a general protocol of copper-catalyzed allylic substitutions using "soft" nucleophiles such as indoles, pyrroles, amines, and 1,3-dicarbonyls has been developed, delivering a large variety of functionalized 1,3-and 1,4-enynes with high levels of regio- and stereoselectivities (67 examples). A range of further transformations of the products can be easily achieved to release various functionalized molecules. A mechanistic rationale with a copper acetylide-bonded allylic cation as the key intermediate that features an outer-sphere nucleophilic attack has been proposed. Additionally, a series of diversified reactivities have been demonstrated, which will inspire further studies.

• 单位
  中国科学院福建物质结构研究所; 广州中医药大学; 中国科学院研究生院; 广东省人民医院