The synthesis of various new 1-aminated-2,5-cyclohexadienes is described. These reagents can be used in radical transfer hydroaminations of unactivated and electron-rich double bonds. With thiols as polarity reversal catalysts good yields are obtained. The radical hydroamination occurs with good to excellent anti-Markovnikov selectivity. Many functional groups such as alcohols, silyl ethers, phosphonates, arylbromides, imides, amides, and also acidic protons are tolerated under the reaction conditions. DFT calculations provide insights into the aromatization of silyl, alkyl, and aminyl substituted cyclohexadienyl radicals to generate the corresponding C-, Si-, and N-centered radicals.