Previously it has been shown that the synthesis of oxacycles can be achieved through the reaction of dialkyl peroxides with ketone enolates (J. Am. Chem. Soc. 2014, 136, 5821-5823). We hypothesized that this reaction could be extended to sulfone- and nitrile-stabilized carbanions. This presentation will discuss the synthesis of peroxide-substituted sulfones and nitriles, and the reactivity of derived carbanions and azaenolates towards formation of sulfone- and nitrile- substituted oxacycles. The purpose of this work was to explore the effects of sulfones as electron withdrawing groups in the formation of oxacycles via an intramolecular reaction on a peroxide substrate. An attack of the sulfonyl carbanion on the dialkyl peroxide electrophile forms a new C-O bond and can be used to create different ring sizes of oxacylces. Over the course of this work, various bases were tested such as n-butyl lithium (n-BuLi), phenyl lithium (PhLi), lithium diisopropylamide (LDA), lithium bis(trimethylsilyl) amide (LiHMDS) and potassium t-butoxide (KOtBu) for the ability to quickly form an alpha sulfonyl stabilized carbanion. Oxacycle rings were synthesized such as the 4-, 5-, and 6-membered rings. Currently, more synthesis is being undertaken exploring different electron withdrawing groups such as nitriles and observing how they affect the intramolecular cyclization of oxacycles.

Peroxide electrophiles for C-O bond formation

249th National Meeting (2015)

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