Represented herein is a simple thiol identified as an
effective
precursor to photochemically form a carbocation. Thanks to the thiyl
radical rapid transformation to disulfide, which serves not only to
stabilize the generated thiyl radical but also to allow the second
electron transfer to form a carbocation. The resulting carbocations,
including primary benzylic, secondary, and tertiary carbocations,
can smoothly couple with nitrogen, oxygen, and carbon nucleophilic
coupling partners as well as complex drug molecules, accompanied by
elemental sulfur formation in air.