The photoinduced anti-Markovnikov hydroamination of olefins
typically
required photocatalysts with a high oxidative ability to initiate
the single-electron process. Herein, we alternatively utilize bis(2,4,6-triisopropylphenyl)
disulfide, an inexpensive reagent with relatively low oxidative ability,
as a photo and hydrogen atom transfer catalyst to achieve intramolecular
hydroamination. The mechanistic studies as well as the DFT calculations
are consistent with a novel process involving N-centered radical generation
through the homolysis of the in situ formed N–S
species and subsequent cyclization. An array of diverse nitrogen-containing
cycles could be obtained.