Synthesis of <i>S</i>,<i>S</i>,<i>O</i>‑Orthoesters and 1,1-Difluoroalkyl Ethers via Reaction of Peroxides with Lithiated 1,3-Dithianes

Alkyl tetrahydropyranyl peroxides (ROOTHP) transfer alkoxide (OR) to lithiated 1,3-dithianes. The derived <i>S</i>,<i>S</i>,<i>O</i>-orthoesters undergo fluorodesulfurization with HF/pyridine and <i>N</i>-bromosuccinamide (NBS) to furnish difluoromethyl ethers. The overall protocol can be applied to synthesis of both terminal (ROCF₂H) and internal (ROCF₂R′) ethers. Application of the same set of reactions to a lithiated tris­(alkylthio)­alkane is shown to generate a trifluoromethyl ether

Synthesis of Alkyl Hydroperoxides via Alkylation of <i>gem</i>-Dihydroperoxides

2-Fold alkylation of 1,1-dihydroperoxides, followed by hydrolysis of the resulting bisperoxyacetals, provides a convenient method for synthesis of primary and secondary alkyl hydroperoxides