Hydroselenation of olefins: elucidating the β-selenium effect.

We report a light-promoted hydroselenation of alkenes with high -Markovnikov selectivity. Blue light activates an aryl diselenide to generate a seleno radical with subsequent addition into an alkene to form a β-seleno carbon radical. Hydrogen atom transfer (HAT) from the selenol to the carbon radical generates the linear selenide with high selectivity in preference to the branched isomer.