Aminopyridine-Borane Complexes as Hydrogen Atom Donor Reagents: Reaction Mechanism and Substrate Selectivity

Abstract

Lewis base-borane complexes are shown to be potent hydrogen atom donors in radical chain reduction reactions. Results obtained in ¹ H, ¹¹ B, and ¹³ C NMR measurements and kinetic experiments support a complex reaction mechanism involving the parent borane as well as its initial reaction products as active hydrogen atom donors. Efficient reduction reactions of iodides, bromides, and xanthates in apolar solvents rely on initiator systems generating oxygen-centered radicals under thermal conditions and pyridine-borane complexes carrying solubilizing substituents. In contrast to tin hydride reagents, the pyridine-boranes reduce xanthates faster than the corresponding iodides.

Keywords: Lewis base; NMR spectroscopy; borane complexes; hydrogen-atom transfer; radical reactions.