Diastereo- and Enantioselective Synthesis of Polyfunctional Cyclic Ketones with Neighboring Quaternary and Tertiary Stereogenic Centers via [2,3]-Wittig Rearrangement

Abstract
The diastereo- and enantioselective synthesis of β-substituted γ,δ-unsaturated cyclic α-hydroxy ketones 4 with neighboring quarternary and tertiary stereogenic centers via asymmetric [2,3]-Wittig rearrangement of SAEP-hydrazones 2 with good overall yields (58-74%), high anti-selectivities (92-94%) and excellent enantiomeric excesses (ee ≥ 96%) is described. The absolute configuration is determined by X-ray structure analysis of the hydrazone 3b and by 1H NMR NOE measurements.

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