Science of Synthesis

Trauner, D., Science of Synthesis, (2008) 32, 551.

Thermodynamic enolates can be formed through equilibration in protic solvents, at higher temperatures, or in the presence of a slight excess of substrate. At equilibrium, the thermodynamically more stable, more highly substituted enolates prevail; some examples are shown in ‌Scheme 4‌. Under thermodynamic conditions, bromo ketone ‌8‌ undergoes selective protonation and alkylation to yield acylbicyclo[3.3.0]octane ‌14‌ (‌Scheme 4‌)[‌7‌] [cf. hydroazulenones ‌9‌, Section ‌32.5.2.1.1.1‌ (‌Scheme 3‌)]. Enones give dienolates with an oxido-substituent in the terminal position under thermodynamic conditions. For example, deprotonation of hexahydronaphthalenone ‌15‌ and alkylation with a soft electrophile yields compound ‌16‌.[‌10‌]

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Meeee [(8eM,8M,8M,8eM)-8-(8,8-Meeeeeeeeeeeeee)-8,8-eeeeeeee-8-eee-8,8,8,8,8,8e-eeeeeeeeeeeeeeeeeee-8e(8M)-ee]eeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee eee eeeeee ‌88‌ (888 ee, 8.8 eeee) ee eee MMM (8 eM) eee eeeee 8.8 M MeMMMM ee MMM (8.8 eM, 8.8 eeee) ee ee. Mee eeee eee eeeeeee eee 88 eee ee ee eeeee eeeee, eee eeeee eeeeeeeeeee (8.888 eM, 8.8 eeee) eee eeeee ee ee. Mee eeeeeee eee eeeeeee eee 8 e ee ee eee M8M (8 eM) eee eeeee. Mee eeeeeee eeeee eee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeeee eeee eeeeee eeee eee. ee MeMe (88 eM), eeeee, eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee [eeeeee eee (88 e), MeMMe/eeeeeee 8:88]; eeeee: 888 ee (88%).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 88e, 888.