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Total synthesis of Tetrodotoxin:
Reference: Sato, K.; Akai, S.; Shoji, H.; Sugita, N.; Yoshida, S.; Nagai, Y.; Suzuki, K.; Nakamura, Y.; Kajihara, Y.; Funabashi, M.; Yoshimura, J.; JOC. 2008, 73, 1234. DOI
Keywords: Diol-1,2 → Ketal • Epoxidation, peracid • Epoxide → Diol • Ketal → Diol-1,2 • Dehydrosulfonoxylation → Vinyl-NO2 • Ketal → Diol-1,2 • Diol-1,2 → Ketal • O-H → O-MOM • Acetal(thio) → Aldehyde • O-H → O-SiPh2tBu • Aldehyde → Alkyl-OH • O-Bn → O-H • Diol-1,2 → Ketal • Epoxide+Azide • Aldehyde → CarboxAcid • Jones oxidation • Lactone-6 • Azide → Amine • Hydrogenation azide • O-SiPh2tBu → O-H • Alkyl-OH → Aldehyde • Ketal → Diol-1,2 • Nef reaction • Nitro → Aldehyde/Ketone • Mechanism • Aldehyde → Cyanohydrin • O-H → O-MOM • Nitrile → Aldehyde • Amine → Guanidine • Diol-1,2 cleavage • Henry reaction • Nitro aldol • Li-Sulfide+Vinyl-NO2 • Vinyl-NO2+Li-R • ConjAdd Li-R • Li-Dichloromethyl+Ketone • O-H → O-Bn •
Reagents: I2 • Acetone (react) • DBU • 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-cr-5 • CrO3, H2SO4 (Jones) • H2, Pd • Fluoride, R4N+ • CrO3Cl·PyH (PCC) • HCl, H2O • Acetic acid, trifluoro • NaOMe • LiCH(SPh)2 • DMSO (solvent) • Cyanide, trimethylsilyl • NEt3 • CH2(OMe)2 • P2O5 • AlHiBu2 • S=C(NHBoc)2 • HgCl2 • Acetic acid • Benzyl-X •

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