Oxidative Rearrangement Of Mida (N-Methyliminodiacetic Acid) Boronates: Mechanistic Insights And Synthetic Applications

Herein we report that coordinative hemilability allows the MIDA ( N-methyliminodiacetic acid) nitrogen to behave as a nucleophile and intramolecularly intercept palladium pi-allyl intermediates. A mechanistic investigation indicates that this rearrangement proceeds through an S(N)2-like displacement at tetrasubstituted boron to furnish novel DABN boronates. Oxidative addition into the N-C bond of the DABN scaffold furnishes borylated pi-allyl intermediates that can then be trapped with a variety of nucleophiles, including in a three-component coupling.