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  • Title: Stereogenic-at-metal Zn- and Al-based N-heterocyclic carbene (NHC) complexes as bifunctional catalysts in Cu-free enantioselective allylic alkylations.
    Author: Lee Y, Li B, Hoveyda AH.
    Journal: J Am Chem Soc; 2009 Aug 19; 131(32):11625-33. PubMed ID: 19630406.
    Abstract:
    Investigations detailed herein demonstrate the ability of chiral bidentate N-heterocyclic carbenes to promote directly-without the need for a Cu salt-site- and enantioselective C-C bond forming reactions. Within this context, catalytic allylic alkylations of various allylic phosphates with dialkylzinc and trialkylaluminum reagents, performed with chiral bidentate imidazolinium salts and in the absence of a Cu salt, are described. The Cu-free transformations deliver products bearing tertiary or (all-carbon) quaternary stereogenic centers with exceptional site- (>98:<2 S(N)2':S(N)2) and high enantioselectivity [up to 97.5:2.5 enantiomer ratio (er)]. A chiral Zn-based N-heterocyclic carbene (NHC) complex, which serves as the catalyst for the enantioselective allylic alkylation reactions, is isolated and fully characterized. Spectroscopic and X-ray crystallographic studies indicate that the sulfonate group within the stereogenic-at-Zn bidentate complexes coordinates syn to the proximal phenyl substituent of the NHC backbone (vs the initially expected anti). Investigations regarding a related NHC-Al complex reveal similar structural attributes. The studies outlined provide a plausible rationale regarding the mechanism of Cu-free allylic alkylation reactions that involve dialkylzinc or trialkylaluminum reagents as well as the previously reported alkylmagnesium halides. On the basis of the research disclosed, it is proposed that bidentate metal-carbene complexes can serve as effective bifunctional catalysts, a critical attribute that differentiates such NHC-based complexes from the corresponding monodentate variants.
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