Total synthesis of Cannabisativine:
| Reference: | Kuethe, J. T.; Comins, D. L. J. Org. Chem., 2004, 69, 5219-5231 DOI |
| Reactions: | CompE+-CarboxAmide/Ketone+M-R • CarboxAmide(Weinreb)+Li-R • Li-Alkynyl+CarboxAmide • Li/H → Li-Alkynyl • Ketone enolate+Pyridinium • Pyridinium+Enolate • Li/H → Li-Vinyl-OR • Li-R → Zn-R • CarboxEster → CarboxAmide(Weinreb) • O-H → O-Bn • Alkyne → Alkane • Si-Vinyl → H-Vinyl • Luche reduction • Ynone → Propargyl-OH • O-H → O-C(O)NR2 • Enone → Enone-α-SeR • Ketene acetal+Enone • Enone-β-Amino+EnolSilane • ConjAdd Ketene acetal • Reductive elimination - Se/OR • Ketone → Alkyl-OH • Luche reduction • CompRed-Ketone/CarboxEster+M-H • CarboxEster → CarboxAcid • CarboxAcid → CarboxAmide • N-C(O)OR → N-H • CompE+-Carbamate/CarboxAmide+H2O • CarboxEster → CarboxAcid • CarboxAcid → CarboxCl • N-H → N-Alkyl • N-H → N-Alkyl • Lactam-9+ • N-SO2R → N-H • O-H → O-SO2Me • CompNu-O-H/O-H+RSO2X • O-Bn → O-H • |
| Reagents: | Chiral auxiliary (alcohol) • Alkynyl-Li • NMe(OMe)-AlMe2 • LiNiPr2 • ZnCl2 • BH4-Na+, CeCl3 • NaH • PMBO-C(=NH)-CCl3 • H2, Pt • Acetic acid, trifluoro • LiN(SiMe3)2 • SePh-Cl • TfOH • Ketene acetal • BF3·OEt2 • BH4-Na+, CeCl3 • S=C(Imid)2 • DMAP • HSnBu3 • Sulfonyl chloride, methane • Hydroxide, potassium • Oxalyl chloride • Hydroxide, potassium • Sulfonyl chloride, methane, NEt3 • Carbonate, potassium • Na°/NH3 • |