Soft Propargylic Deprotonation: Designed Ligand Enables Au-Catalyzed Isomerization of Alkynes to 1,3-Dienes

被引：82
|
作者：
Wang, Zhixun [1 ]
Wang, Yanzhao [1 ]
Zhang, Liming [1 ]
机构：
[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 25期
基金：
美国国家科学基金会;
关键词：
BOND-FORMING REACTIONS; COUPLING REACTIONS; SUZUKI-MIYAURA; ARYL CHLORIDES; C-N; PALLADIUM; TRIETHYLAMINE; PHOSPHINES; ACIDITIES; COMPLEXES;
D O I：
10.1021/ja503909c
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
By functionalizing the privileged biphenyl-2-ylphosphine with a basic amino group at the rarely explored 3' position, the derived gold(I) complex possesses orthogonally positioned "push" and "pull" forces, which enable for the first time soft propargylic deprotonation and permit the bridging of a difference of >26 pK(a) units (in DMSO) between a propargylic hydrogen and a protonated tertiary aniline. The application of this design led to efficient isomerization of alkynes into versatile 1,3-dienes with synthetically useful scope under mild reaction conditions.
引用
收藏
页码：8887 / 8890
页数：4
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