期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 144, 期 23, 页码 10483-10494出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c02745
关键词
-
资金
- Institute for Chemical Reaction Design and Discovery
- JSPS KAKENHI [17H06370, 18H03907]
- JSPS [16J01410, 19J20823]
- Program for Leading Graduate Schools
- Grants-in-Aid for Scientific Research [16J01410, 19J20823] Funding Source: KAKEN
A new series of C-1-symmetric P-chirogenic bisphosphine ligands have been developed, which showed high performance in a copper(I)-catalyzed asymmetric borylation reaction. Computational studies highlighted the importance of the highly rigid phosphine conformation in achieving high stereo- and product-selectivities.
A new series of C-1-symmetric P-chirogenic bisphosphine ligands of the type (R)-5,8-Si-Quinox-tBu(3)(Silyl = SiMe3, SiEt3, SiMe2Ph) have been developed. The bulky silyl modulators attached to the ligand backbone fix the phosphine substituents to form rigid chiral environments that can be used for substrate recognition. The ligand showed high performances for a copper(I)-catalyzed asymmetric borylative cyclopropanation of bulky silyl-substituted allylic electrophiles to afford higher disfavored 1,2-cis-silyl-boryl-cyclopropanes than the other possible isomers, trans-cyclopropane and allylboronate (up to 97% yield; 98% ee; cis/trans = >99:1; cyclopropane/allylboronate = >99:1 Detailed computational studies suggested that the highly rigid phosphine conformation, which is virtually undisturbed by the steric interactions with the bulky silyl-substituted allyl electrophiles, is key to the high stereo- and product-selectivities. Furthermore, the detailed computational analysis provided insight into the mechanism of the stereoretention or -inversion of the chiral alkylcopper(I) intermediate in the intramolecular cyclization.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据