Recent experiments have revealed the reactions of peroxides with nucleophilic carbon to be an effective synthetic pathway to ethers. We have used B3LYP calculations to characterize the mechanisms of these novel reactions. Carbon nucleophiles under consideration include alkyl metal reagents, enolates, and enol ethers. In the bimolecular reaction of CH3M (M = Li, Na, or K) with dialkyl peroxides, the K+ counterion consistently gives the lowest activation enthalpy: B3LYP/6-31+G(d,p) gas-phase calculations predict that K+-containing transition structures are 1-3 kcal/mol lower in energy than Li+ structures and 3-5 kcal/mol lower in energy than Na+ structures. This is a consequence of the large size of K+, which facilities simultaneous coordination of the peroxide group and the transferring methyl anion, and the electrostatic stabilization afforded by the high charge density on Li+. We will report results on spiroether formation from cyclic enolates reacting with tethered peroxides and the impact of Lewis acids such as BF3, TiCl4, SnCl4, and BF3OEt2 in activating enol ethers for reaction with peroxides.

Quantum chemical studies of ether formation with peroxide reagents

253rd National Meeting (2017)

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