Krishnakumar Sachidanandan, Monish A. Ansari, Savini Senanayake, Athul Joshy, Sébastien Laulhé
We report a metal-free, light-driven platform that expands amine chemical space using amino acid derivatives and simple alkanes as carbon-based synthons. The transformation demonstrates an underexplored sequential decarboxylative-dehydrogenative process, employing in situ generated aryl radicals to activate a broad range of C(sp 3 )–H bonds. Representative amino acids, including glycine, alanine, valine, and leucine derivatives undergo efficient decarboxylative coupling with activated and unactivated C(sp 3 )–H bonds affording structurally diverse amine products. This strategy underscores the untapped potential of simple next-generation bioderived and hydrocarbon building blocks for light-enabled C(sp 3 )–C(sp 3 ) cross-couplings as a complementary strategy to reductive amination.