Science of Synthesis

Zeh, J.; Hiersemann, M., Science of Synthesis: Stereoselective Synthesis, (2011) 3, 372.

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]

Me eeeeeee ee eee eeeeeeeeeee ee ee eeeeeee eee-Meee eeeeeeeeeeeee ee eee eeeeeeeeeeee ee e eeeeeeeeee eeeeee eeeeeeeeeee eeeeee ee ee eeeeeeeeeeeee eeeeeeeee eeeeee eeeeeeeeeee ee eeeeeeee ee ‌Meeeee 88‌.[‌88‌] Mee 8-eeeeeee-8,8-eeeee ‌888‌ ee eeeeeeeee ee e eeeeee eeeeeeeeeeeeeeeeee eeeeee eeeeeeeeee ee eeeeeeee ‌888‌ eeeee Meeeeeeeʼe eeeeee eeeeeeeee eeeeeee (M,M)-‌888‌. Meeeeeeeeeeee ee ‌888‌ eeee eeeeeeeee eeee-eeeeeeee ee eee eeeeeeee ee 88-eeeee-8 eeeee eee eeeeeeeeeeeee eeeeeeee, eeeee eeeeeeeee eee-Meee eeeeeeeeeeeee ee e eee eeeeeeeeeee, eeeeeeeeee eee eee eeeee-eeee eeeeeeeeee-eeeee eeeeeeeee ‌888‌. Mee eeeeeeeeeee eeeeee ee eee [8,8]-eeeeeeeeeee eeeeeeeeeeeee eeeeeee eee eeeeeeeeee ee eee eeee-eeeeeeeeee 8,8-eeeeeeeee eeeeeeee. Mee eeeeeeee eeeeee eeee ee eee eeeeeeeeee eeeeeee ‌888‌ ee eeeeeee eeeeeeeeee ee eeeeeeeeee eee eeeeeeeee eeeeeeeee ee eeeeeee eee eeeeeeeee eeeee ‌888‌, eeeee eee ee eeeeeeeee eeee eee eeeeeeeeeee eeeeee ee (−)-eeeeeeeee (‌88‌).

‌Meeeee 88‌ Meeeeee Mee-Meee Meeeeeeeeeeee ee eee Meeee Meeeeeeee ee (−)-Meeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

(8M,8M,8′M,8M,8M,8e′M)-8e′-Meeee-8-(eeeeeeeee)-8,8-eee(eeee-eeeeeeeeeeeeeeeeeee)-8′-eeeeee-8′,8′,8′-eeeeeeeeee-8′,8′,8′,8e′-eeeeeeeeeeeeeee[eeeeeeeeeeee-8,8′-eeeee]-8′(8′M)-eee (‌888‌); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee 88-eeeee-8 (88 ee, 8.88 eeee) eee e-MeMM (88 ee, 8.88 eeee) ee MMM (8.8 eM) eee eeeeeee ee 8 °M eee 88 eee, eee eeee e eeee ee eeeeee ‌888‌ (88 ee, 8.888 eeee) ee MMM (8.88 eM) eee eeeee eeeeeeee eeee 8 eee. Mee eeeeeeeee eeeeeee eee eeeeeee ee 8 °M eee 8 e. Mee eeeeeeee eee eeeeeeee ee eee eeeeeeee ee M8M (8 eM), eee eee eeeeeee eee eeeeeee eeee Me8M (8 eM). Mee eeeeee eeee eeeeeeeee, eee eee eeeeeee eeeee eee eeeee (MeMM8) eee eeeeeeeeeeee ee eeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (8% Me8M ee eeeeeee/MeMMe 8:8) ee eeee e eeeeeeeee eee; eeeee: 88.8 ee (88%).

References