Herein, we report a rhodium catalyzed directing‐group free regioselective C−H allylation of simple arenes. Readily available gem‐difluorinated cyclopropanes can be employed as highly reactive allyl surrogates via a sequence of C−C and C−F bond activation, providing allyl arene derivatives in good yields with high regioselectivity under mild conditions. The robust methodology enables facile late‐stage functionalization of complex bioactive molecules. The high efficiency of this reaction is also demonstrated by the high turnover number (TON, up to 1700) of the rhodium catalyst on gram‐scale experiments. Preliminary success on kinetic resolution of this transformation is achieved, providing a promising access to enantio‐enriched gem‐difluorinated cyclopropanes.

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.

Efficient palladium recovery from high level liquid wastes (HLLW) is of increasing priority for sustainable development and addressing issues in radioactive wastes treatment. However, searching for robust materials for palladium...

Herein, we report an effective method to offer chiral gem-difluorinated cyclopropanes containing an all-carbon quaternary stereocenter by rhodium-catalyzed stereoablative kinetic resolution. The activation of a sterically hindered all-carbon quaternary C–C bond through oxidative addition with a chiral rhodium complex is proposed as the enantiodetermining step. A wide range of gem-difluorinated cyclopropanes can be obtained with excellent ee values (ee = 87% to >99.9%), which are demonstrated to be useful chiral fluorine-containing building blocks by a series of postfunctionalizations.

The control of linear/branched selectivity is one of the major focuses in transition-metal catalyzed allyl-allyl cross-coupling reactions, in which the bond connection occurs at the terminal site of both the...