The bimolecular reaction between a monoperoxyacetal or perester with an organolithium reagent can be modeled by the B3LYP/6-31G(d) quantum chemical method to determine viable reaction pathways to a trifluoromethoxyl ether. Mapping of both reaction schemes with respect to relative enthalpies led to the discovery of many energetically competitive outcomes and interconversion between various reaction pathways. The transition structures for these pathways had high enthalpic barriers to formation and generally resulted in much lower enthalpy product complexes. Theoretical studies suggest more information is needed to find a direct route to trifluoromethyl ethers but confirm findings by the Dussault group that this etherification reaction is not an effective synthetic approach.

Targeted trifluoromethoxyl transfer: Lithiated alkyl reagents with nucleophilic carbon

255th National Meeting (2018)

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