A new Co-catalyzed sequential C–C and C–F activation of gem-difluorinated cyclopropanes (gem-FCPs) to form nucleophilic fluoroallylcobalt, followed by addition to aldehydes, is reported. The protocol features the regioselective cleavage of dual chemical bonds of readily available gem-FCPs to prepare easily separable linear (Z)- and (E)-fluorinated homoallylic alcohols with a broad scope. This discovery established a new strategy for the efficient transformation of gem-FCPs as well as the synthesis of challenging fluorinated homoallylic alcohols.

A palladium‐catalyzed chemoselective coupling of readily available bicyclo[1.1.1]pentanyl alcohols (BCP−OH) with various halides is reported, which offers expedient approaches to a wide range of cyclobutanone and β,γ‐enone skeletons via single or double C−C activation. The chemistry shows a broad substrate scope in terms of both the range of BCP−OH and halides including a series of natural product derivatives. Moreover, dependency of reaction chemodivergence on base additive has been investigated through experimental and density functional theory (DFT) studies, which is expected to significantly enrich the reaction modes and increase the synthetic potential of BCP−OH in preparing more complex molecules.

A palladium‐catalyzed chemoselective coupling of readily available bicyclo[1.1.1]pentanyl alcohols (BCP−OH) with various halides is reported, which offers expedient approaches to a wide range of cyclobutanone and β,γ‐enone skeletons via single or double C−C activation. The chemistry shows a broad substrate scope in terms of both the range of BCP−OH and halides including a series of natural product derivatives. Moreover, dependency of reaction chemodivergence on base additive has been investigated through experimental and density functional theory (DFT) studies, which is expected to significantly enrich the reaction modes and increase the synthetic potential of BCP−OH in preparing more complex molecules.

Herein a study of chemoselective C-C cleavage of bicyclo[1.1.1]pentanyl alcohols (BCP-OH) is reported. The highly ring-strained BCP-OH was shown to be particularly reactive to deliver cyclobutanone derivatives via base-mediated single C-C cleavage as well as α,β-unsaturated ketones by palladium-catalyzed dual C-C cleavage.