The stereoselective construction of all carbon quaternary stereogenic centers remains both an important and challenging area of investigation. In this context, the synthesis of acyclic quaternary centers remains arguably the greatest challenge, despite the development of a number of elegant approaches over the last decade. Among these methods, enolate alkylation represents a particularly powerful synthetic strategy, which provides one of the most fundamentally important carbon-carbon bond forming reactions in synthetic organic chemistry. Nevertheless, the stereocontrolled construction of acyclic quaternary carbon centers <i>via</i> enolate alkylation has a number of inherent limitations. For instance, the ability to regioselectively form an enolate from an unsymmetrical ketone, polyalkylation <i>via</i> enolate equilibration and the necessity to employ simple electrophiles adversely impacts the chiral and achiral versions of this venerable process. Additionally, this process generally requires a specific enolate geometry, since the origin of enantioselectivity is often defined by a combination of enolate geometry and π-facial selectivity in the alkylation. The presentation will focus on two entirely new approaches for the asymmetric construction of acyclic quaternary carbon stereogenic centers.

New allylic alkylation reactions: Asymmetric construction of acyclic quaternary carbon stereogenic centers

249th National Meeting (2015)

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