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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 α‐tertiary boronic esters. The intermediate boronate complexes undergo the desired 1,2‐rearrangement of the carbon‐based...
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