Site-Divergent Alkenyl C–H Fluoroallylation of Olefins Enabled by Tunable Rhodium Catalysis
Yaxin Zeng, Han Gao, Yulei Zhu, Zhong‐Tao Jiang, Gang Lü, Ying Xia
Abstract
The unique properties of the fluorine-containing compounds and their widespread applications raise the demand for dependable synthetic methods on the precise introduction of fluorine-containing substituents into organic molecules. Herein, a site-divergent fluoroallylation of olefins that can incorporate the fluoroallyl motif into different alkenyl C–H sites is disclosed. gem-Difluorinated cyclopropanes are employed as fluoroallyl sources via rhodium-catalyzed C–C bond activation. This strategy can provide two regioisomeric fluorinated skipped dienes in good yields with excellent site-selectivity. The resulting products can serve as useful building blocks to access various fluorine-containing molecules and are isosteric to β, γ-unsaturated amides, which are promising to be exploited in medicinal chemistry. Mechanistic studies revealed that the electronic property of rhodium catalysts is crucial for the controllable excellent site-selectivity, providing more insights beyond the methodology on tuning the selectivity of metal catalysts.