Ring-Opening Lithiation-Borylation of 2-Trifluoromethyl Oxirane: A Route to Versatile Tertiary Trifluoromethyl Boronic Esters

摘要

Stereogenic trifluoromethyl-substituted carbon centers are highly sought-after moieties in pharmaceutical and agrochemical discovery. Here, we show that lithiation-borylation reactions of 2-trifluoromethyl oxirane give densely functionalized and highly versatile trifluoromethyl-substituted alpha-tertiary boronic esters. The intermediate boronate complexes undergo the desired 1,2-rearrangement of the carbon-based group with complete retentive stereospecificity, a process that was only observed in non-polar solvents in the presence of TESOTf. Although the trifluoromethyl group adversely affects subsequent transformations of the alpha-boryl group, Zweifel olefinations provide trifluoromethyl-bearing quaternary stereocenters substituted with alkenes, alkynes and ketones.