Direct Observation of Reactive Intermediates by Time-Resolved Spectroscopy Unravels the Mechanism of a Radical-Induced 1,2-Metalate Rearrangement.

Radical-induced 1,2-metalate rearrangements of boronate complexes are an emerging and promising class of reactions that allow multiple new bonds to be formed in a single, tunable reaction step. These reactions involve the addition of an alkyl radical, typically generated from an alkyl iodide under photochemical activation, to a boronate complex to produce an α-boryl radical intermediate. From this α-boryl radical, there are two plausible reaction pathways that can trigger the product forming 1,2-metalate rearrangement: iodine atom transfer (IAT) or single electron transfer (SET).