title: Synthesis of S,S,O-orthoesters and 1,1-difluoroalkyl ethers via reaction of peroxides with lithiated 1,3-dithianes.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588-0304, United States.
authors.forename: Shiva K.
authors.initials: SK
authors.lastname: Kyasa
authors.forename: Patrick H
authors.initials: PH
authors.lastname: Dussault
mesh_terms: D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000737:chemistry*; D015394:Molecular Structure; D010545:Peroxides / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry
chemical_list: D004987:Ethers; D006571:Heterocyclic Compounds; D010545:Peroxides; D011725:Pyridines; C012947:1,3-dithiane; C023666:pyridine