(η6-Arene)ruthenium half-sandwich complexes are highly active and stereoselective catalysts in the enantioselective desymmetrization of 2-n- butyl-4,7-dihydro-1,3-dioxepin to give 2-n-butyl-4,5-dihydro-1,3-dioxepin. Enantioselectivities up to 61% ee were achieved. The temperature and solvent dependence of the catalysis as well as the activation of the catalyst were investigated.
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