The stereoselective synthesis of quaternary stereocentre containing compounds is a persistent challenge in organic synthesis. This is particularly challenging in the enantioselective formation of multiple stereocentres, given the need to control both relative and absolute stereochemistry. This limits access to highly substituted sp<sup>3</sup> rich scaffolds that are desirable synthetic targets in drug discovery and natural products chemistry. The work presented in this poster enables stereoselective access to cyclopentanoids with up to three contiguous quaternary centres in 3-4 steps (workups) from a chiral oxazolidinyl ynamide via alkyne carbometallation and Nazarov reaction. As the utility of a synthetic method is dependent on both the scope of the method and the accessibility of the precursors, conditions for both the convergent, stereoselective conversion of ynamides to divinyl ketones and subsequent asymmetric Nazarov reaction have been developed. This method enables the formation of a range of multi-quaternary centre containing cyclopentanoids, including those with heteroaromatic substitution, with high torquoselectivity (dr&gt;20:1). Removal of the chiral oxazolidinone auxiliary is achieved through reductive cleavage of the Cα-N bond.

Asymmetric synthesis of multi-quaternary centre containing cyclopentanoids via the Nazarov reaction

254th National Meeting (2017)

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