Total synthesis of Calicheamicinone New:
| Reference: | Smith, A. L.; Hwang, C.-K.; Pitsinos, E.; Scarlato, G. R.; Nicolaou, K. C. J. Am. Chem. Soc. 1992, 114, 3134-3136. DOI |
| Reactions: | O-H → O-SiMe2tBu • CompNu-O-H/O-H+R3Si-X • O-SiMe2tBu → O-H • O-C(O)R → O-H • O-MEM → O-H • O-C(O)R → O-H • Si-Alkynyl → H-Alkynyl • O-H → O-SiEt3 • Si-Alkynyl → H-Alkynyl • O-H → O-Piv • O-H → O-SiEt3 • O-Piv → O-H • O-SiEt3 → O-H • Lactone → Lactol • Lactol → Allyl-OH • Mitsunobu → SR • Alkyl-OH → Alkyl-SR • B-Allyl-Ipc+Aldehyde • Aldehyde+B-Allyl (asym) • O-H → O-C(O)R • Alkyl-OH → Aldehyde • Aldehyde → Oxime • Oxime → Nitrile oxide • Nitrile oxide Cycloaddition • Cyclohexane • Jones oxidation • Alkyl-OH → Ketone • Ketone+Li-Alkynyl • CompE+-Ketone/Imine+M-R • O-H → O-C(O)R • Alkyl-OH → Aldehyde • Wittig-carboxymethyl → EnoateEster • CompE+-Ketone/CarboxEster+Wittig • Pd/H-Alkynyl+Vinyl-X • Oxime → Amine • Amine → Imide • Li/H → Li-Alkynyl • Li-Alkynyl+Aldehyde • Cyclodecane • Alkyl-X → Alkyl-OC(O)R • Lactone-6 • Phthalimide → Amine • N-H → N-C(O)OR • S-C(O)R → S-H • S-H → S-SSR • O-H → O-SiMe2tBu • CompNu-O-H/O-H+R3Si-X • Ketal → Enone • |
| Reagents: | Allyl-B(Ipc)2 • SiMe2tBu-Cl • Benzoyl chloride • DMAP • Fluoride, R4N+ • DMSO, (COCl)2 (Swern) • NEt3 • NH2OH • Hypochlorite, sodium • NaOMe • CrO3, H2SO4 (Jones) • Alkynyl-Li • Acetic anhydride • ZnBr2 • DMSO, (COCl)2 (Swern) • PPh3=CH-CO2R • NaOMe • SiEt3-OTf • Lutidine • Alkynyl-SiR3 • Pd(PPh3)4 • CuI • Mo(CO)6 • NaOMe • Acetic anhydride • KN(SiMe3)2 • Sulfonyl chloride, methane • NEt3 • DMAP • SiO2 • O=CCl2 • Triphosgene • AlHiBu2 • BH4-Na+ • Piv-Cl • SiEt3-OTf • AlHiBu2 • Thiol, acetyl • PPh3, DEAD • AlHiBu2 • TsOH • Chiral auxiliary (boronate) • |