Reactivity of 1,3-enyne MIDA boronates: exploration of novel 1,2-alkyne shift via gem-difluorination

Abstract

The discovery of a new class of heteroatom-rich boron-containing molecules (BCMs) and iterative cross-coupling (ICC) partners created a toolbox for future drug developments using organoboron compounds. Herein, we report the potential utility of 1,3-enyne MIDA boronates to access diverse gem-difluoro MIDA boronates via novel 1,2-alkyne shift. This unique reactivity of 1,3-enyne MIDA boronates offers facile access to previously challenging β-difluorinated alkyl borons. Furthermore, we demonstrated the synthesis of various novel furan-based BCMs via 5-endo-dig cyclization and iterative coupling partners via copper-catalyzed hydroboration and platinum-catalyzed diboration reaction.