Alkyl tetrahydropyranyl peroxides (ROOTHP) transfer alkoxide (OR) to lithiated 1,3-dithianes. The derived S,S,O-orthoesters undergo fluorodesulfurization with HF/pyridine and N-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. (Chemical Equation Presented).
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry