Remote Chirality Transfer within a Coordination Sphere by the Use of a Ligand Possessing a Concave Cavity

The possibility to enhance the effect of a modest chiral element in a metal ligand by the use of a
second ligand possessing a concave cavity has been examined for the examples of 1,3- and 1,4-chirality
transfer within the metal coordination sphere. Complexation of Ru(C60Me5)Cl(CO)2 with (R)-prophos
[(R)-1,2-bis(diphenylphosphino)propane] took place with excellent diastereoselectivity to give a
configurationally stable chiral-at-metal complex, Ru(C60Me5)Cl((R)-prophos). This complex was converted,
with good to perfect diastereoselectivity, into a variety of cationic complexes, [Ru(C60Me5)((R)-prophos)L][SbF6] (L = MeCN, tBuCN, methacrolein, acetone, CO, BnNC, 2,6-Me2C6H3NC), and a vinylidene
complex, [Ru(C60Me5)(CCPhH)((R)-prophos)][SbF6]. The chirality transfer to the reactants reacting
in the outer sphere of the coordination resulted in an asymmetric Diels−Alder reaction, albeit with modest
selectivity.