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 3 to 10 5 times lower than that of tin and silicon radicals and only slightly higher than alkyl radicals. This challenges the belief that α-aminoalkyl radicals are as reactive as tin radicals. The study on the solvent effect indicates that the XAT reaction of α-aminoalkyl radicals does not involve a highly polarized transition state, suggesting that the kinetic polar effect in this XAT process is not as significant as previously believed. The present study provides a reliable XAT reactivity scale for α-aminoalkyl radicals, which is crucial for designing XAT reactions and understanding their mechanisms.