Traditional etherification methods rely on a nucleophilic oxygen and an electrophilic carbon. However, we have been interested in an inversion of this approach: by employing a dialkyl or silyl peroxide as a source of electrophilic oxygen and reacting it with a nucleophilic carbon, we are able to supplement current C-O bond forming reactions and allow access to synthetically challenging ethers. We have applied this ‘flipped’ approach to the synthesis of tertiary bicylic ethers through the intramolecular reaction of an enolate anion with silyl peroxides or peroxyacetals. Interestingly, we have observed differing reactivity and arguably different reaction modes that seem strongly dependent on the enolate’s metal counter ion and the type of peroxide. In this work we have been able to demonstrate a useful and complementary etherification method as well as beginning to both elucidate the mechanism of action and demonstrate how seemingly small variations may strongly impact reaction mode.

Flipped etherification method: Reactions between enolates and peroxides

251st National Meeting (2016)

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