Long‐Wavelength Light‐Induced Group 13–15 Elementalization Reactions of Alkenes/Alkynes

Abstract We present di‐ tert ‐butyl peroxide (DTBP)‐catalyzed long‐wavelength light‐induced Group 13, 14, and 15 elementalizations of alkenes and alkynes, through in situ production of tert ‐butyl radicals, followed by a hydrogen‐atom‐transfer process generating silyl, germyl, stannyl, alkyl, boryl, and phosphoryl radicals. This mild and photosensitizer‐free methodology employing blue (450 nm)/green (530 nm)/orange (600 nm) LEDs affords high chemoselectivity and broad functional group tolerance compared to conventional use of shorter‐wavelength light. Synthetic, spectroscopic, and computational data are consistent with a vibration‐mediated photolysis mechanism of DTBP involving electronic excitation from vibrationally excited ground states (S 0 μ n ) to the excited state (S 0 μ n →S n transitions), driven by ultraweak absorption of long‐wavelength visible light.