A Chiral Sulfoxide-Ligated Ruthenium Complex for Asymmetric Catalysis: Enantio- and Regioselective Allylic Substitution

The
design and synthesis of a novel chiral sulfoxide-ligated cyclopentadienyl
ruthenium complex is described. Its utility as an asymmetric variant
of [CpRu­(MeCN)3]­PF6 is demonstrated through
its ability to function in the branched-selective asymmetric allylic
alkylation of phenols and carboxylic acids. Water has also been shown
to act as a competent nucleophile in this reaction to generate branched
allyl alcohols with good regio- and enantioselectivities.