Combination of Tetrabutylammonium Iodide (TBAI) with tert‐Butyl Hydroperoxide (TBHP): An Efficient Transition‐Metal‐Free System to Construct Various Chemical Bonds

In this account, we describe our recent progress on transition‐metal‐free‐catalyzed cross‐coupling reactions using tetrabutylammonium iodide (TBAI) as the catalyst and tert ‐butyl hydroperoxide (TBHP) as the oxidant. A rich variety of important organic compounds including α‐acyloxy ethers, tert ‐butyl peresters, allylic esters, amides, α‐amino nitriles, fully substituted pyrazoles, N ‐sulfonyl formamidines, α‐amino acid esters, cyanomethyl esters, N ‐nitrosamines, and 3‐acyloxy‐2,3‐dihydrobenzofurans have been successfully achieved in high chemoselectivity. Mechanistic studies suggested that TBAI could decompose TBHP to t BuO . and t BuOO . or be oxdized to (hypo)iodite by TBHP.