A reagent for heteroatom borylation, including iron mediated reductive deoxygenation of nitrate yielding a dinitrosyl complex

Abstract

4,4′-Bipyridyl is shown to be a catalyst for transfer of pinacolboryl groups from (Bpin)₂ to nitrogen heterocycles and to Me₃SiN₃. Using stoichiometric (Bpin)₂(pyrazine) or (Bpin)₂(bipyridine) in an analogous manner, an aromatic nitro group is deoxygenated and subsequently borylated, and four-fold deoxygenation of (DIM)Fe(NO₃)₂(MeCN) to yield the dinitrosyl complex (DIM)Fe(NO)₂ is facile. The co-product O(Bpin)₂ is the quantitative fate of the removed oxo groups. With borylation of both nitrogen heterocycles and doubly deoxygenating two nitrates coordinated to a single metal center, broad spectrum methodology is demonstrated.