Oxidative Rearrangement of MIDA (<i>N</i>-Methyliminodiacetic Acid) Boronates: Mechanistic Insights and Synthetic Applications
Sherif J. Kaldas, Chieh‐Hung Tien, Gabriel dos Passos Gomes, Stephanie Meyer, Martynas J. Širvinskas, Hayden Foy, Travis Dudding, Andrei K. Yudin
Abstract
Herein we report that coordinative hemilability allows the MIDA (N-methyliminodiacetic acid) nitrogen to behave as a nucleophile and intramolecularly intercept palladium π-allyl intermediates. A mechanistic investigation indicates that this rearrangement proceeds through an SN2-like displacement at tetrasubstituted boron to furnish novel DABN boronates. Oxidative addition into the N–C bond of the DABN scaffold furnishes borylated π-allyl intermediates that can then be trapped with a variety of nucleophiles, including in a three-component coupling.
Topics & Concepts
ChemistryNucleophileSN2 reactionOxidative phosphorylationBoronCoupling (piping)Oxidative coupling of methaneStereochemistryCombinatorial chemistryOrganic chemistryCatalysisBiochemistryMechanical engineeringEngineeringOrganoboron and organosilicon chemistryCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization Methods