Methyl Radical Addition Reactions to C═X Double Bonds.

ABSTRACT: Radical additions to olefins and related π-systems are essential tools in the modern synthetic toolbox for forging C-C and C-X bonds. We report a systematic DFT study (ZORA-(U)OLYP/TZ2P) on methyl radical (H₃C^•) additions to H₂C═X substrates, where X is varied across elements from the tetrel (group 14: C, Si, Ge), pnictogen (group 15: N, P, As), and chalcogen (group 16: O, S, Se) groups. Our analysis reveals clear periodic trends: addition barriers at carbon decrease, and those at X increase from tetrels to chalcogens; reaction energies become less favorable across a period but more favorable down a group. Regioselectivity favors addition at X except for X = CH₂, NH, and O, where carbon attack dominates─consistent with experimental data. These tr

SUBMITTER: Hordijk Y 

PROVIDER: S-EPMC12322914 | biostudies-literature | 2025 Aug

REPOSITORIES: biostudies-literature