An unprecedented Pd-catalyzed regioselective activation of gem-difluorinated cyclopropanes induced by C-C bond cleavage is reported. It provides a general and efficient access to a variety of 2-fluoroallylic amines, ethers, esters, and alkylation products in high Z-selectivity, which are important skeletons in many biologically active molecules. In addition, the transformation represents the first general application of gem-difluorinated cyclopropanes as reaction partners in transition-metal-catalyzed cross-coupling reaction.

Monofluoroalkenes normally act as metabolically stable bioisosteres for amide groups (−NH–CO−) and have widespread applications in drug discovery. Additionally, they are widely used as building blocks in organic synthesis. In this study, the Cu/Pd-catalyzed cis-borylfluoroallylation of alkynes was achieved, providing a modular and general tactic for the preparation of monofluorinated alkene scaffolds with high regioselectivity and stereoselectivity. Moreover, an array of synthetic building blocks can be generated by downstream transformations.

Herein, we describe a novel copper-catalyzed epoxide opening reaction with gem-diborylmethane. Aliphatic, aromatic epoxides as well as aziridines are converted to the corresponding γ-pinacolboronate alcohols or amines in moderate to excellent yields. This new reaction provides beneficial applications for classic epoxide substrates as well as interesting gem-diborylalkane reagents.