Synthesis Of Alkyl Hydroperoxides Via Alkylation Of \u3ci\u3egem\u3c/i\u3e-Dihydroperoxides

Two-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

A Mild One-Pot Conversion of Alkenes into Amines through Tandem Ozonolysis and Reductive Amination

The selective reduction of hydroperoxyacetals to aldehydes by sodium triacetoxyborohydride provides the basis for a mild one-pot synthesis of amines from alkenes. Includes Supplementary Materials

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 Ethers via Reaction of Carbanions and Monoperoxyacetals

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 sp3 and sp2 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

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