Abstract
The ligand exchange reactions of [(C2H4)2Rh(acac)] in benzene and [(C2H4)2RhCl]2 in CH2Cl2 with 4-methyl-4-trichloromethyl-2,5-cyclohexadiene-1-one occur with 100%exo-stereoselectivity. The similar process with 4-methyl-4-trichloromethyl-1-(4,4-dimethyl-4,6-dioxocyclohexylidene)-2,5-cyclohexadiene (trienedione) is strictlyexo-stereospecific only if [(C2H4)2Rh(acac)] in benzene is used, while in the case of [(C2H4)2RhCl]2 in CH2Cl2, it proceeds with anendo-stereoselectivity of 43%. An explanation for these facts has been suggested that assumes that the metal atom initially attacks the central double bond in the trienedione, which is removed from the area of main steric hindrance. The subsequent metallotropic rearrangement of the resulting ethylene-triene intermediate gives rise to the final η4-coordinated π-diene structures.
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