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Abstract
Ruthenium complexes, in particular cyclopentadienyl ruthenium (<small>ii</small>) derivatives, catalyze a vast number of transformations in the field of homogenous catalysis. Herein we describe the first synthesis of efficient chiral cationic cyclopentadienyl ruthenium (<small>ii</small>) catalysts and their application in enantioselective cycloisomerizations yielding 4H-pyrans. A tremendous counterion effect on the selectivity was observed and subsequently explored, giving rise to a complementary set of neutral cyclopentadienyl ruthenium (<small>ii</small>) complexes able to catalyze asymmetric cyclobutene formations.
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