CF 3 -containing diborylated compounds were successfully prepared from readily available CF 3 bearing 1,3-enynes, without fluorine elimination, and subsequently, several useful fluorine-containing molecules were synthesized. These transformations exhibit a high degree of regio-, stereo-, and chemoselectivity, affording CF 3 containing E-1,3-, Z-1,3and Z-1,4-diborylated olefins. Control experiments and density functional theory calculations provide explanations for the observed selectivities.

A divergent strategy for precise construction of SCF2H or SeCF2H groups on heteroarenes generated in situ from CF3-containing 1,3-enynes was developed. Reactions of readily available 1,3-enynes with S8 and ClCF2H provided 3-SCF2H-4-CF3-thiophenes via a cascade thiophene construction/selective C3 position thiolation/difluoromethylthiolation process, as did a series of 3-SeCF2H-4-CF3-selenophenes by similar strategies. The plausible radical annulation process for the construction of the thiophene ring and difluorocarbene generated in situ was confirmed by experiment.

A mild, transition metal-free, diborane-mediated deoxygenation of nitro groups was discovered that in situ generates nitrosoarene reactive intermediates. This new reactivity mode of B2pin2 was leveraged to construct indoles from o-nitrostyrenes through a reductive-cyclization reaction that exhibits a Hammett ρ-value of +0.97 relative to σpara values. Our new deoxygenation reaction is efficient, practical, and scaleable, enabling access to a broad range of indoles.

Abundant multi-borylated compounds, such as alkyl 1,2-bis(boronates), gem-diborylalkanes and 1,1,2-tris(boronates) are constructed via the base-promoted DBP strategies, which can undergo selective protodeboronation, giving many borylated molecules.