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Cooperative Bimetallic Asymmetric Catalysis: Comparison of a Planar Chiral Ruthenocene Bis-Palladacycle to the Corresponding Ferrocene

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posted on 06.06.2014, 00:00 authored by Tina Hellmuth, Stefan Rieckhoff, Marcel Weiss, Konstantin Dorst, Wolfgang Frey, René Peters
Cooperative asymmetric catalysts often offer advantages in terms of activity, stereoselectivity, and generality as compared to more traditional single point activation catalysts. In cooperative bimetallic catalysis, the intermetallic distance is a crucial parameter for the outcome of a reaction and an optimal synergy of both metal centers. We have recently developed a number of catalytic asymmetric reactions, which are efficiently catalyzed by a planar chiral ferrocene based bispalladacycle and for which the cooperativity of two Pd centers has already been demonstrated. To get more insight into the role of the Pd/Pd distance in such metallocene bismetallacycles, in the present study a corresponding ruthenocene based Pd2-complex has been prepared by the first direct diastereoselective biscyclopalladation of a chiral ruthenocene ligand. In addition, the first highly diastereoselective direct monocyclopalladation of a homochiral ruthenocene is reported. The effect of the increased Cp/Cp distance within the ruthenocene bispalladacycle has been examined in four catalytic asymmetric applications: the aza-Claisen rearrangement of Z-configured allylic N-aryltrifluoroacetimidates, the direct 1,4-addition of α-cyanoacetates to enones, a tandem azlactone formation/1,4-addition to enones and a tandem reaction to form quaternary α-aminosuccinimides by in situ azlactone formation, 1,4-addition to a nitroolefin, and a Nef-type nitro-to-carbonyl transformation as key steps. For each reaction studied, it was found that with some substrates the ferrocene based catalyst is superior, whereas for other substrates the ruthenocene backbone is more favorable. The ruthenocene based bispalladacycle can thus be considered to be a useful and complementary alternative for cooperative bimetallic catalysis.