Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis

We report stereodivergent allylic
substitution reactions of allylic
esters with prochiral enolates derived from azaaryl acetamides and
acetates to form products from addition of the enolates at the most
substituted carbon of an allyl moiety with two catalysts, a chiral
metallacyclic iridium complex and a chiral bis­phosphine-ligated
copper­(I) complex, which individually control the configuration of
the electrophilic and nucleophilic carbon atoms, respectively. By
simple permutations of enantiomers of the two catalysts, all four
stereoisomers of products containing two stereogenic centers were
synthesized individually with high diastereoselectivity and enantioselectivity.
A variety of azaaryl acetamides and acetates bearing pyridyl, benzothiazolyl,
benzoxazolyl, pyrazinyl, quinolinyl and isoquinolinyl moieties were
all found to be suitable for this transformation.