Total synthesis of Herboxidiene A:
| Reference: | Smith, N. D.; Kocienski, P. J.; Street, S. D. A. Synthesis 1996, 652. DOI |
| Reactions: | Ti-Allyl+Aldehyde • Felkin-Anh • Li/I → Li-Alkyl • Metalate rearrangement (Cu) • Julia-Kocienski • CompE+-Aldehyde/CarboxEster+M-R • Li-Sulfone+Aldehyde • Li/H → Li-Vinyl-OR • Li/H → Li-Allyl (asym) • Li-R → Ti-R • Cu-Vinyl+Alkyl-X • Alkyl-X+Cu-R • O-SiEt3 → O-H • O-SiMe2tBu → O-H • O-But → O-H • O-SiMe2tBu → O-H • O-H → O-PMB • Dehydroalkoxylation → Yne • Li/H → Li-Alkynyl • Li-Alkynyl+Chlorocarbonate • Alkyne → Alkane • CarboxEster → Aldehyde • HWE → EnoateEster • ConjAdd M-OR • Ether-6 • HWE → EnoateEster • Alkyl-OH → Ketone • Mitsunobu → SR • Alkyl-OH → Alkyl-SR • Epoxidation, V • Pd-Deallylation • CarboxEster → CarboxAcid (allyl) • Li-R → Sn-R • Li/Sn → Li-Vinyl • CarboxAcid → Aldehyde • |
| Reagents: | Allyl-Li • Ti(OiPr)4 • Lactaldehyde • Vinyl-Li • BuLi(tert) • SnBu3-Cl • Vinyl-SnR3 • Alkyl-Li • BuLi(tert) • CuI • LiCHR-Sulfonyl • MeI • LiCHR-Sulfonyl • MeOTf • Pyridine, 2,6-di-tBu • Alkyl-Li • HMPA (solvent) • HF·Py • PPh3, DEAD • Thiol, benzothiazole • H2O2, Mo • LiNiPr2 • Vinyl-Li • SiMe3-OTf • Vinyl-Li • BuLi(tert) • BuLi(n) • O=C(OMe)Cl • H2, Pd • AlHiBu2 • P(O)(OR)2CH2-C(O)R' • NaH • DDQ • Fluoride, R4N+ • KOtBu • CrO3Cl·PyH (PCC) • P(O)(OR)2CH2-C(O)R' • NaH • PMBO-C(=NH)-CCl3 • Vilsmeier reagent • Acetic acid, trifluoro • AlH(OtBu)3-Li+ • HF·Py • Hydroperoxide, tbutyl - V • Pd(PPh3)4 • |