Silicon-oriented regio- and enantioselective rhodium-catalyzed hydroformylation

• Published in: Nature communications 2018-05, Vol.9 (1), p.2045-9, Article 2045
• Main Authors: You, Cai, Li, Xiuxiu, Yang, Yuhong, Yang, Yu-Sheng, Tan, Xuefeng, Li, Shuailong, Wei, Biao, Lv, Hui, Chung, Lung-Wa, Zhang, Xumu
• Format: Article
• Language: English
• Subjects: 119/118; 140/131; 140/58; 639/638/403/935; 639/638/549/972; 639/638/77/883; Alkenes; Asymmetry; Catalysis; Computer applications; Density functional theory; Enantiomers; Humanities and Social Sciences; multidisciplinary; Oxygen; Regioselectivity; Rhodium; Science; Science (multidisciplinary); Silicon; Silicon substrates
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-018-04277-7

Hydroformylation of 1,2-disubstituted alkenes usually occurs at the α position of the directing heteroatom such as oxygen atom and nitrogen atom. By contrast, to achieve hydroformylation on the β 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 β position (relative to the silicon heteroatom) and enantioselectivity. In a synthetic sense, we achieve the asymmetric hydroformylation on the β 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. Hydroformylation of 1,2-disubstituted alkenes usually occurs at the α position of the directing heteroatom. Here, the authors report the asymmetric rhodium-catalyzed hydroformylation of 1,2-disubstituted alkenylsilanes with excellent regioselectivity at the β position (relative to the silicon heteroatom) and enantioselectivity.