Total synthesis of Calarene:
| Reference: | Coates, R. M.; Shaw, J. E. J. J. Am. Chem. Soc. 1970, 92, 5657 DOI |
| Reactions: | Ketone → EnAmine • Robinson annulation, enamine • EnAmine ConjAdd • Cyclohexenone • Bicyclo(440) • Enone → Ketal(thio) • CompE+-Ketone/Enone+glycol • Ketal(thio) → CH2 • Ketone → CH2 • Claisen acylation, carbonate • Ketone enolate+Carbonate • Li-Me+KetoEster • CompE+-CarboxEster/Ketone+M-R • Pyrazoline synthesis • Cyclopropane • Azo fragmentation • Bicyclo(410) • Dehydration → Enone • |
| Reagents: | Pyrrolidine • Methyl vinyl ketone • Acetate, sodium • Acetic acid • TsOH • H2, RaNi • NaH • O=C(OR)2 • Me-Li • Hydrazine • Hydroxide, potassium • HCl, MeOH • |