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A chiral version of the Cp*Ru(COD)Cl complex equipped with an atropchiral cyclopentadienyl (Cp x ) ligand enables [2+2]-cycloadditions between bicyclic olefins and alkynes with excellent reactivity and enantioselectivity. A streamlined synthesis of the Cp x  ligand by a C–H functionalisation approach is shown. The chloride counterion of the neutral Cp x Ru II  complex is essential for enantioselectivity.

Neutral chiral cyclopentadienyl Ru(ii)Cl catalysts enable enantioselective [2+2]-cycloadditions