title: Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals.
abstract: Although transfer of electrophilic alkoxyl ("RO+") from organic peroxides to organometallics offers a complement to traditional methods for etherification, application has been limited by constraints associated with peroxide reactivity and stability. We now demonstrate that readily prepared tetrahydropyranyl monoperoxyacetals react with sp(3) and sp(2) organolithium and organomagnesium reagents to furnish moderate to high yields of ethers. The method is successfully applied to the synthesis of alkyl, alkenyl, aryl, heteroaryl, and cyclopropyl ethers, mixed O,O-acetals, and S,S,O-orthoesters. In contrast to reactions of dialkyl and alkyl/silyl peroxides, the displacements of monoperoxyacetals provide no evidence for alkoxy radical intermediates. At the same time, the high yields observed for transfer of primary, secondary, or tertiary alkoxides, the latter involving attack on neopentyl oxygen, are inconsistent with an SN2 mechanism. Theoretical studies suggest a mechanism involving Lewis acid promoted insertion of organometallics into the O-O bond.
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.affiliation: Department of Chemistry, Macalester College , Saint Paul, Minnesota 55105, United States.
authors.forename: Rebecca N
authors.initials: RN
authors.lastname: Meier
authors.affiliation: Department of Chemistry, Macalester College , Saint Paul, Minnesota 55105, United States.
authors.forename: Ruth A
authors.initials: RA
authors.lastname: Pardini
authors.affiliation: Department of Chemistry, Macalester College , Saint Paul, Minnesota 55105, United States.
authors.forename: Tristan K
authors.initials: TK
authors.lastname: Truttmann
authors.affiliation: Department of Chemistry, Macalester College , Saint Paul, Minnesota 55105, United States.
authors.forename: Keith T
authors.initials: KT
authors.lastname: Kuwata
authors.affiliation: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588-0304, United States.
authors.forename: Patrick H
authors.initials: PH
authors.lastname: Dussault
mesh_terms: D000080:Acetals / Q000737:chemistry*; D000838:Anions / Q000737:chemistry*; D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D010545:Peroxides / Q000737:chemistry*
chemical_list: D000080:Acetals; D000838:Anions; D004987:Ethers; D010545:Peroxides