Silicon-oriented regio- and enantioselective rhodium-catalyzed hydroformylation.

ABSTRACT: Hydroformylation of 1,2-disubstituted alkenes usually occurs at the ? position of the directing heteroatom such as oxygen atom and nitrogen atom. By contrast, to achieve hydroformylation on the ? 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 ? position (relative to the silicon heteroatom) and enantioselectivity. In a synthetic sense, we achieve the asymmetric hydroformylation on the ? 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.

SUBMITTER: You C 

PROVIDER: S-EPMC5966446 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature