Total synthesis of Neocarzinostatin (Part 1):
| Reference: | Myers, A. G.; Glatthar, R.; Hammond, M.; Harrington, P. M.; Kuo, E. Y.; Liang, J.; Schaus, S. E.; Wu, Y.; Xiang, J.-N. J. Am. Chem. Soc. 2002, 124, 5380. DOI (Part 2) |
| Reactions: | Propargyl-OH → Ynone • Si-Alkynyl → H-Alkynyl • Ketal → Diol-1,2 • O-SiPh2tBu → O-H • Si-Alkynyl → H-Alkynyl • Enal → Allyl-OH • Li-Alkynyl+Aldehyde • Li/H → Li-Alkynyl • Wittig-propargyl → Enyne • Sharpless epoxidation • Sharpless epoxidation • Li-Alkynyl+Ketone • Enone+Li-R • Li/H → Li-Alkynyl • Si-Alkynyl → H-Alkynyl • CompE+-Si-Alkynyl/Si-O+H2O • Li-Alkynyl+Aldehyde • Li/H → Li-Alkynyl • Felkin-Anh Chelation • Cyclononane • Bicyclo(730) • Selenolate+Enone • ConjAdd-Silylation • Selenoxide-Ei → Enone • Ketone → Enone • Claisen acylation, formate • EnolSilane+Orthoester • Diol-1,2 → Ketal • O-H → O-SiPh2tBu • Alkyl-OH → Aldehyde-α-OR • |
| Reagents: | Alkynyl-Li • Cr2O7·2PyH (PDC) • PPh3=CH-Alkynyl • Carbonate, potassium • HCl, H2O • SiPh2tBu-Cl • Hydroperoxide, tbutyl - Ti • Epoxide • HF·NEt3 • Propenyl-OR • LiN(SiMe3)2 • Fluoride, R4N+ • AlHiBu2 • Hydroperoxide, tbutyl - Ti • Dess-Martin • LiN(SiMe2Ph)2 • Chloride, lithium • SePh-SiMe3 • SiMe3-OTf • Orthoformate • H2O2 • |