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Updated: Aug 13, 2026

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)
Published on: June 20, 2014
Selective alkane C-H-bond functionalizations utilizing oxidative single-electron transfer and organocatalysis
Peter R Schreiner1, Andrey A Fokin
1Institut für Organische Chemie, Justus-Liebig-University, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany. prs@org.chmie.uni-giessen.de
Abstract:
Alkane C-H-bond functionalization methods not utilizing metal-catalysis are discussed based on experimental and computational data, beginning with molecule-induced homolysis (reactions of alkanes with dioxiranes). Electrophilic reactions are elaborated next with an emphasis on mechanistic details that reveal that many so-called electrophilic C-H or C-C-bond insertions can be rationalized by electron-transfer reactions (inner sphere, H-coupled, and outer sphere). Finally, radical functionalizations utilizing carbon-centered (relatively stable) radicals generated under organocatalytic (phase-transfer catalysis, PTC) conditions are presented as valuable alternatives to other radical-chain alkane functionalizations. The remarkable chemo- and regioselectivities of these PTC radical reactions and the tolerance of high strain in certain aliphatic hydrocarbons make them particularly useful for laboratory-scale halogenations, in particular, iodinations of unactivated alkane C-H-bonds.
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