Silicon-oriented regio- and enantioselective rhodium-catalyzed hydroformylation

作者：Cai You, Xiuxiu Li, Yuhong Yang, Yusheng Yang, Xuefeng Tan, Shuailong Li, Biao Wei, Hui Lv, Lung Wa Chung, Xumu Zhang · 发表于：Nature Communications · 年份：2018 · DOI：10.1038/s41467-018-04277-7 · 被引用次数：40 · 研究领域：Organometallic Complex Synthesis and Catalysis、Organoboron and organosilicon chemistry、Carbon dioxide utilization in catalysis

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.