Total synthesis of Callystatin A:
| Reference: | Marshall, J. A.; Bourbeau, M. P. J. Org. Chem. 2002, 67, 2751. DOI |
| Reactions: | O-PMB → O-H • Allyl-OH → Allyl-Br • Appel → Br • Allyl-X → Allyl-PRn • EnoateEster → Allyl-OH • EnoateEster → Allyl-OH • Allyl-OH → Enal • O-H → O-SiMe3 • O-SiMe3 → O-H • CompE+-Si-O/Si-O+H2O • O-SiMe2tBu → O-H • Sn-Allenyl+Aldehyde • Aldehyde+Sn-R • Felkin-Anh Chelation • Li-Alkynyl+Epoxide • Epoxide+Li-R • Li/H → Li-Alkynyl • Pd/B-Alkyl+Vinyl-X • Wittig-carboxymethyl → EnoateEster • Hydrostannation Alkyne • Seyferth-Gilbert homologation • Aldehyde → Alkyne • Alkyne → Ene-cis (Lindlar) • HWE → EnoateEster-cis • Wittig-allyl → Diene • Li/I → Li-Alkyl • Li-R → B-R • Borane+Li-R • Alkyne → Alkane • Sn-Vinyl → I-Vinyl • Alkyne → Ene-cis (Lindlar) • Zn-Allenyl/Propargyl+Aldehyde • Aldehyde+Zn-R • Felkin-Anh • O-H → O-SiMe2tBu • Alkyl-OH → Aldehyde-α-OR • Alkyl-OH → Alkyl-I • Ozonolysis • Allyl-OH → EnoateEster • Lactone-6 • Alkyl-OH → Ketone • O-Bn → O-H • Alkyl-OH → Aldehyde • O-H → O-SiMe2tBu • O-SiMe3 → O-H • CompE+-Si-O/Si-O+H2O • |
| Reagents: | Epoxide • Alkynyl-Li • BF3·OEt2 • SiMe2tBu-Cl • H2, Pd • DDQ • DMSO, (COCl)2 (Swern) • P(O)(OCH2CF3)2CHR-C(O)OMe • PPh3, CBr4 • PBu3 • AlHiBu2 • KOtBu • TsOH·Py • PPh3, I2 • Alkyl-Li • Allenyl-SnR3 • BF3·OEt2 • SiMe2tBu-OTf • H2, Pd • DMSO, (COCl)2 (Swern) • O3 • PPh3=C(Me)-CO2R • AlHiBu2 • MnO2 • Diazophosphonate • SiMe3-Cl • TsOH·Py • HSnBu3 • I2 • BuLi(tert) • B(OMe)BBN • PdCl2(dppf) • Dess-Martin • HF·NEt3 • MnO2 • Alkyl-BR2 • PdCl2(PPh3)2 • Vinyl-SnR3 • Imidazole • Imidazole • Allenyl-ZnX • H2, Pd • PBu3 • Lutidine • BuLi(n) • 15-crown-5 • |