Total Syntheses

Reaction scheme for total synthesis of the natural product Roflamycoin (Part 1)
Total synthesis of Roflamycoin (Part 1):
Reference:Rychnovsky, S. D.; Khire, U. R.; Yang, G. J. Am. Chem. Soc. 1997, 119, 2058. DOI (Part 2) (Part 3)
Reactions:Diol-1,2 cleavage • O-H → O-SiMe2tBu • Diol-1,2 cleavage • Diol-1,3 → Ketal • Diol-1,2 → Ketal • Ketal(thio) → Ketone • Petasis reagent • Ketone → C=CH2 • B-Allyl-Ipc+Aldehyde • Aldehyde+B-Allyl (asym) • Mukaiyama Aldol • Aldol-Si • Ketene acetal+Aldehyde • Li-Ether+Epoxide • Epoxide+Li-R • Li/Sn → Li-Dithiane • Hydroboration → Alkyl-B • Alkene cleavage • Alkene cleavage • CarboxEster → Aldehyde • Li-Dithiane+Alkyl-X • Alkyl-X+Li-R • Pd/B-Alkyl+Vinyl-X • Aldehyde → Cyanohydrin • Diol-1,3 → Ketal • Li-Dithiane+Epoxide •
Reagents:BuLi(n) • Me2C(OMe)2 • Sulfonic acid, Camphor • Hg(ClO4)2 • TiCp2Me2 (Petasis) • OsO4, NMO • Sulfonic acid, Camphor • Me2C(OMe)2 • BH-BBN • Pd(PPh3)4 • Hydroxide, sodium • OsO4, NMO • Periodate, sodium • Allyl-B(Ipc)2 • H2O2, NaOH • SiMe2tBu-OTf • OsO4, NMO • Periodate, sodium • Ketene acetal • AlHiBu2 • Cyanide, trimethylsilyl • Sulfonic acid, Camphor • Me2C(OMe)2 • Carbonate, calcium • Ti(OR)4 • Chiral catalyst (diol) • Chiral auxiliary (boronate) • Epoxide • BF3·OEt2 • Alkyl-BR2 • Alkyl-BR2 • Lutidine •