Stereoselective Direct Chlorination of Alkenyl MIDA Boronates: Divergent Synthesis of E and Z α‐Chloroalkenyl Boronates

The individual molecules of α‐chloroalkenyl boronates include both an electrophilic C−Cl bond and a nucleophilic C−B bond, which makes them intriguing organic synthons. Reported herein is a stereodivergent synthesis of both E and Z α‐chloroalkenyl N ‐methyliminodiacetyl (MIDA) boronates through the direct chlorination of alkenyl MIDA boronates using t BuOCl and PhSeCl reagents, respectively. Both reaction processes are stereospecific and the use of sp³‐B MIDA boronate is the key contributor to the reactivity. The synthetic value of the boronate products was also demonstrated.