Abstract
Terminal or electron-deficient alkynes had been widely applied in transition-metal-free (TM-free) borylation with diboron reagents, allowing the construction of various vinylboronate reagents. By contrast, borylative addition to electronic unbiased triple bonds remained challenging in the TM-free approach. To address this issue, we developed base-promoted borylation of internal propargylic alcohols in ionic liquid medium affording structurally variable vinylboronates.