Photoinduced C(sp<sup>3</sup>)–H Chalcogenation of Amide Derivatives and Ethers via Ligand-to-Metal Charge-Transfer
Ben Niu, Krishnakumar Sachidanandan, María Victoria Cooke, Taylor E. Casey, Sébastien Laulhé
Abstract
A photoinduced, iron(III) chloride-catalyzed C–H activation of N-methyl amides and ethers leads to the formation of C–S and C–Se bonds via a ligand-to-metal charge transfer (LMCT) process. This methodology converts secondary and tertiary amides, sulfonamides, and carbamates into the corresponding amido-N,S-acetal derivatives in good yields. Mechanistic work revealed that this transformation proceeds through a hydrogen atom transfer (HAT) involving chlorine radical intermediates.
Topics & Concepts
ChemistryAmideLigand (biochemistry)MetalCharge (physics)StereochemistryMedicinal chemistryPhotochemistryOrganic chemistryReceptorBiochemistryPhysicsQuantum mechanicsSulfur-Based Synthesis TechniquesOrganoselenium and organotellurium chemistryCatalytic C–H Functionalization Methods