Y. Morisaki et al., Ruthenium-catalyzed allylic substitution of cyclic allyl carbonates with nucleophiles. Stereoselectivity and scope of the reaction, ORGANOMETAL, 18(23), 1999, pp. 4742-4746
CpRuCl(cod)/NH4PF6 (Cp = cyclopentadienyl, cod = 1,5-cyclooctadiene) is an
effective catalyst system for the allylic substitution of cyclic allyl carb
onates with nucleophiles. This catalyst system enables the first investigat
ion of the stereochemical course of the ruthenium-catalyzed allylic substit
ution reaction, in which the reaction proceeds with an overall retention of
configuration. The stoichiometric reaction of trans-5-(methoxycarbonyl)cyc
lohex-2-enyl chloride with Cp*RuCl(cod) (Cp* = pentamethylcyclopentadienyl)
gave the unexpected complex Cp*Ru(eta(6)-C6H5CO2Me)(+) by the rapid dehydr
ohalogenation/dehydrogenation of the desired Cp*RuCl2-(eta(3)-C6H8CO2Me) co
mplex.