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3.7.2.2 The Anionic Oxy-Cope Rearrangement

DOI: 10.1055/sos-SD-203-00213

Zeh, J.; Hiersemann, M.Science of Synthesis: Stereoselective Synthesis, (20113372.

C3-Hydroxy-substituted 1,5-dienes provide a mechanistically intriguing rate-accelerating effect that renders the 3-oxy-Cope rearrangement irreversible and thereby synthetically useful, provided that the initially formed enol undergoes enol-to-keto tautomerization.[‌37‌] Frequently, the 3-hydroxy group is deprotonated to provide an oxyanion, which leads to an even more pronounced rate acceleration in the anionic oxy-Cope rearrangement.[‌38‌]

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