Abstract: | The ring‐opening reactions of N‐methyliminodiacetyl (MIDA) α‐chloroepoxyboronates with different nucleophiles allow the modular synthesis of a diverse array of organoboronates. These include seven types of α‐functionalized acylboronates and seven types of borylated heteroarenes, some of which are difficult‐to‐access products using alternative methods. The common synthons, α‐chloroepoxyboronates, could be viably synthesized by a two‐step procedure from the corresponding alkenyl MIDA boronates. Mild reaction conditions, good functional‐group tolerance, and generally good efficiency were observed. The utility of the products was also demonstrated. |