Total synthesis of Dynemycin A Model New:
| Reference: | Porco Jr., J. A.; Schoenen, F. J.; Stout, T. J.; Clardy, J.; Schreiber, S. L. J. Am. Chem. Soc. 1990, 112, 7410-7411. DOI Wood, J. L.; Porco Jr., J. A.; Taunton, J.; Lee, A. Y.; Clardy, J.; Schreiber, S. L. J. Am. Chem. Soc. 1992, 114i, 5898-5900. DOI Total synthesis of Dynemycin A: Taunton, J.; Wood, J. L.; Schreiber, S. L. J. Am. Chem. Soc. 1993, 115, 10378-10379. DOI. (Synthesis of Dynemycin A) |
| Reactions: | Yamaguchi lactonization • Lactone-9+ • Pd/Sn-Vinyl+Aryl-X • Pyridinium+M-R • Si-Alkynyl → H-Alkynyl • O-SiMe2tBu → O-H • Pd/H-Alkynyl+Vinyl-X • Diels-Alder, Intram, Ene • Lactone-5 • Bicyclo(440)-aza • Cyclodecane • Benzylic oxidation → Benzyl-OR • Allyl-OH → Allyl-H • Epoxidation, peracid • Epoxidation, peracid • Benzylic oxidation → Benzyl-OR • Lactone epimerization • Allyl-OH → Allyl-H • Mechanism • Diazene rearrangement • Diimide+Alkene • Lactone → Lactone-α-OR • Lactone → Alkyl-OH • Diol-1,2 → Carbonate • Alkyl-OH → Aldehyde • Acetal → CarboxAcid • Carbonate → Diol-1,2 • CarboxAcid → CarboxEster • |
| Reagents: | Vinyl-SnR3 • Pd(PPh3)4 • O=C(OMe)Cl • Alkynyl-MgX • Alkynyl-SiR3 • Vinyl-Br • Acrylate • Fluoride, R4N+ • Pd(PPh3)4 • CuI • Hydroxide, lithium • Benzoyl chloride, 2,4,6-trichloro • NEt3 • DMAP • Ceric ammonium nitrate • HSiEt3 • AlEt2-Cl • Peracetic acid, trifluoro • Na2HPO4 • BH4-Li+ • KN(SiMe3)2 • MoOPH • O=CCl2 • Dess-Martin • Chlorite, sodium • Hydroxide, lithium • Diazomethane • Periodate, sodium • DBU • Ceric ammonium nitrate • AlMeCl2 • Hydrazine • Triphosgene • Perbenzoic acid, 3-chloro • |