.gif)
Total synthesis of Tedanolide, 13-Deoxy- (Part 1):
| Reference: | Smith, A. B.; Adams, C. M.; Barbosa, S. A. L.; Degnan, A. P. J. Am. Chem. Soc 2003, 125, 350. DOI (Part 2) (Part 3) |
| Reactions: | O-C(O)R → O-H • O-H → O-C(O)R • O-C(O)R → O-H • B-Allyl-Tartrate+Aldehyde • Aldehyde+B-Allyl (asym) • Wittig-alkyl → Ene-cis • Hydroboration → Alkyl-OH • CompRed-Alkene/Alkene+M-H • Diol-1,2 → Ketal • Alkyl-OH → Aldehyde • Alkyl-OH → Alkyl-I • O-PMB → O-H • Corey-Fuchs • Fritsch-Buttenberg-Wiechell • Hydrostannation Alkyne • Li/I → Li-Vinyl • Sn-Vinyl → I-Vinyl • Alkyl-OH → Aldehyde • CompOx-Alkyl-OH/Sulfide+DMSO • Li/H → Li-Alkynyl • Li-Alkynyl+Alkyl-X • CarboxEster(thio) → Aldehyde • Hydrogenolysis Acyl-SR • Aldol-B-Evans • CarboxAmide enolate+Aldehyde (asym) • O-H → O-SiMe2tBu • CarboxAmide(Evans) → CarboxEster(thio) • O-SiMe2tBu → O-H • Reductive etherification • O-H → O-PMB • Alkyl-OH → Aldehyde • Aldol-B-Evans • CarboxAmide enolate+Aldehyde (asym) • CarboxAmide(Evans) → Alkyl-OH • Diol-1,3 → Acetal • O-H → O-Me • Ketal → Diol-1,2 • O-H → O-C(O)R • CompNu-O-H/O-H+RC(O)X • O-H → O-SiiPr3 • Li-Vinyl+Aldehyde • O-H → O-SEM • O-C(O)R → O-H • O-H → O-C(O)R • CompNu-O-H/O-H+RC(O)X • Allyl-OH → Enal • Alkene → Diol-1,2 • Wittig-carboxymethyl → EnoateEster • Aldol-B-Evans • CarboxAmide enolate+Aldehyde (asym) • Alkene cleavage • CompOx-Alkene/Alkene+OsO4 • O-H → O-SiiPr3 • CarboxAmide(Evans) → Alkyl-OH • O-H → O-C(O)R • |
| Reagents: | Crotyl-B(tartrate) • Chiral auxiliary (boronate) • Carbonate, potassium • TsOH·Py • BH-BBN • Acetic anhydride, NEt3 • DDQ • Dess-Martin • PPh3=CH-Me • Carbonate, potassium • MeI • H2O2, NaOH • Me2C(OMe)2 • DMSO, (COCl)2 (Swern) • BuLi(n) • BuLi(tert) • HSnBu3 • I2 • PdCl2 • MeI • BuLi(tert) • Vinyl-Li • Chiral auxiliary (amide-Evans) • B(OTf)Bu2 • SiMe2tBu-OTf • Thiolate, ethyl • HSiEt3 • Chiral auxiliary (amide-Evans) • Chiral auxiliary (amide-Evans) • B(OTf)Bu2 • BH4-Li+ • Fluoride, R4N+ • MeI • AlHiBu2 • DMSO, Py·SO3 (Parikh-Doering) • Chiral auxiliary (amide-Evans) • NaH • TsOH·Py • Acetyl chloride • Carbonate, potassium • SiiPr3-OTf • SEM-Cl • Chiral auxiliary (amide-Evans) • PPh3=C(Me)-CO2R • DMSO, (COCl)2 (Swern) • B(OTf)Bu2 • SiEt2iPr-OTf • BH4-Li+ • Acetic anhydride • OsO4, NMO • Periodate, sodium • Chiral auxiliary (amide-Evans) • PPh3=CBr2 • PPh3, CBr4 • |