Date of this Version
New Method for Synthesis of Alkyl Hydroperoxides: There are a number of methods reported for synthesis of alkyl hydroperoxides, but most of them suffer either from poor yields or the formation of unwanted side products. I will be discussing new methodology for efficient synthesis of pure samples of 1° and 2° alkyl hydroperoxides via alkylation of readily available cyclododecanone 1,1-dihydroperoxide followed by hydrolysis of the resulting bis peroxyacetals.
Peroxide Electrophiles for Synthesis of Functionalized Ethers: Peroxides are underexplored functional groups as precursors for C-O bond formation and ether synthesis. The reactivity of dialkyl peroxides towards organometallics such as alkyl lithium and magnesium reagents is known. However, there has been little application of this reaction to C-O bond formation due to limitations in the reactivity of available reagents for alkoxide transfer. We have studied the reactivity of a variety of dialkyl peroxides, alkyl/silyl peroxides, and monoperoxyacetals towards simple organolithium and organomagnesium reagents and found that thermally stable 2-tetrahydropyranyl peroxides enable efficient and highly selective transfer of 1°, 2° and 3° alkoxide (RO) groups to carbanions to form the corresponding ethers. The method was applied to synthesis of a variety of functionalized ethers, including S,S,O-orthoesters, difluoroethers, mixed O,O-acetals, and cyclopropyl ethers. The observed results are discussed in terms of possible mechanisms for C-O bond formation.
Adviser: Patrick H. Dussault