Overestimated Halogen Atom Transfer Reactivity of α-Aminoalkyl Radicals

Halogen atom transfer (XAT) is a versatile method for generating carbon radicals. Recent interest has focused on α-aminoalkyl radicals as potential XAT reagents, previously reported to exhibit reactivity comparable to tin radicals. Utilizing an advanced time-resolved EPR technique, the XAT reactions between α-aminoalkyl radicals and organic halides were examined, allowing direct observation of the process through EPR spectroscopy and analysis of radical kinetics. Second-order rate constants for these reactions were determined, with some validated using transient absorption spectroscopy. The key finding is that the reactivity of α-aminoalkyl radicals in XAT reactions is 10