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No vacancy: Fully substituted dienones that are highly polarized by a vinylogous carbonate group were found to undergo a remarkably rapid and diastereospecific Nazarov cyclization that led to cyclopentenones with vicinal all‐carbon‐atom quaternary centers (see example; SEM=2‐(trimethylsilyl)ethoxymethyl, Tf=trifluoromethanesulfonyl).
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