Silicon-oriented regio- and enantioselective rhodium-catalyzed hydroformylation

You, Cai1,2; Li, Xiuxiu1,2; Yang, Yuhong3; Yang, Yu-Sheng1,2; Tan, Xuefeng3; Li, Shuailong1,2; Wei, Biao1,2; Lv, Hui1,2,4; Chung, Lung-Wa3; Zhang, Xumu1,2,3

2018-05-23

10.1038/s41467-018-04277-7

Nature Communications   影响因子和分区

2041-1723

Hydroformylation of 1,2-disubstituted alkenes usually occurs at the a position of the directing heteroatom such as oxygen atom and nitrogen atom. By contrast, to achieve hydroformylation on the beta position of the heteroatom is a tough task. Herein, we report the asymmetric rhodium-catalyzed hydroformylation of 1,2-disubstituted alkenylsilanes with excellent regioselectivity at the beta position (relative to the silicon heteroatom) and enantioselectivity. In a synthetic sense, we achieve the asymmetric hydroformylation on the beta position of the oxygen atom indirectly by using the silicon group as a surrogate for the hydroxyl. Density functional theory (DFT) calculations are carried out to examine energetics of the whole reaction path for Rh/YanPhos-catalyzed asymmetric hydroformylation and understand its regioselectivity and enantioselectivity. Our computational study suggests that the silicon group can activate the substrate and is critical for the regioselectivity.

SCI

英语

NI论文

通讯

Important Sci-Tech Innovative Project of Hubei Province[2015ACA058]

Science & Technology - Other Topics

Multidisciplinary Sciences

WOS:000432792100021

NATURE PUBLISHING GROUP

Web of Science

1.Wuhan Univ, Minist Educ, Key Lab Biomed Polymers, Wuhan 430072, Hubei, Peoples R China
2.Wuhan Univ, Coll Chem & Mol Sci, Wuhan 430072, Hubei, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
4.Wuhan Univ, Coll Chem & Mol Sci, Minist Educ, Engn Res Ctr Organosilicon Cpds & Mat, Wuhan 430072, Hubei, Peoples R China

You, Cai,Li, Xiuxiu,Yang, Yuhong,et al. Silicon-oriented regio- and enantioselective rhodium-catalyzed hydroformylation[J]. Nature Communications,2018,9.

You, Cai.,Li, Xiuxiu.,Yang, Yuhong.,Yang, Yu-Sheng.,Tan, Xuefeng.,...&Zhang, Xumu.(2018).Silicon-oriented regio- and enantioselective rhodium-catalyzed hydroformylation.Nature Communications,9.

You, Cai,et al."Silicon-oriented regio- and enantioselective rhodium-catalyzed hydroformylation".Nature Communications 9(2018).