Total synthesis of Tetrodotoxin (Sato):
| Reference: | Sato, K.; Akai, S.; Shoji, H.; Sugita, N.; Yoshida, S.; Nagai, Y.; Suzuki, K.; Nakamura, Y.; Kajihara, Y.; Funabashi, M.; Yoshimura, J.; J. Org. Chem. 2008, 73, 1234. DOI |
| Reactions: | Ketal → Diol-1,2 • Ketal → Diol-1,2 • O-H → O-SiPh2tBu • Epoxide+M-N3 • Azide+Epoxide • O-SiPh2tBu → O-H • Ketal → Diol-1,2 • N-Boc → N-H • Nef reaction • Alkyl-NO2 → Ketone • Mechanism • O-H → O-MOM • Diol-1,2 cleavage • Nitro aldol • Li-Sulfide+EneNitro • EneNitro+Li-R • ConjAdd Li-R • Li-Dichloromethyl+Ketone • Nitro aldol • Cyclohexane • Azide → Amine • Hydrogenation azide • Aldehyde → CarboxAcid • Jones oxidation • Lactone-6 • Guanidine synthesis • Nitrile → Aldehyde • Dehydrosulfonoxylation → EneNitro • Diol-1,2 → Ketal • O-H → O-MOM • Acetal(thio) → Aldehyde • Aldehyde → Alkyl-OH • O-Bn → O-H • Diol-1,2 → Ketal • Epoxidation, peracid • Epoxide → Diol • O-H → O-Bn • Alkyl-OH → Ketone • Wittig-methyl • Aldehyde → Cyanohydrin • Diol-1,2 → Ketal • Alkyl-OH → Aldehyde • |
| Reagents: | I2 • Acetone (react) • DMSO, (CF3CO)2O • PPh3=CH2 • Perbenzoic acid, 3-chloro • Hydroxide, sodium • NaH • Acetic acid • Periodate, sodium • MeNO2 • Sulfonyl chloride, methane, NEt3 • Acetic acid • Bicarbonate, sodium • Me2C(OMe)2 • CH2(OMe)2 • P2O5 • NBS • SiPh2tBu-Cl • BH4-Na+ • KOtBu • Acetic acid • H2, Pd • Me2C(OMe)2 • LiNiPr2 • Azide, sodium • 15-crown-5 • CrO3, H2SO4 (Jones) • H2, Pd • Fluoride, R4N+ • CrO3Cl·PyH (PCC) • HCl, H2O • Acetic acid, trifluoro • NaOMe • LiCH(SR)2 • DMSO (solvent) • Cyanide, trimethylsilyl • NEt3 • CH2(OMe)2 • P2O5 • AlHiBu2 • S=C(NHBoc)2 • HgCl2 • Acetic acid • Benzyl-X • DBU • |