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A visible‐light‐mediated photoredox‐catalyzed semipinacol‐type rearrangement proceeding via 1,2 alkyl migration was developed. In this transformation, trifluoromethylation of the CC bond of α‐(1‐hydroxycycloalkyl)‐substituted styrene derivatives is followed by ring expansion of the 1‐hydroxycycloalkyl group to deliver novel cycloalkanones with all‐carbon quaternary centers. The reaction proceeds...
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