Total synthesis of Stipiamide, 6,7-Dehydro:
| Reference: | Zeng, X.; Zeng, F.; Negishi, E. Org. Lett. 2004, 6, 3245-3248. DOI |
| Reactions: | Pd/Zn-Alkynyl+Vinyl-X • Pd/Zn-Vinyl+Vinyl-X • Si-Alkynyl → H-Alkynyl • Li/H → Li-Alkynyl • Li-R → Zn-R • Li-R → Zn-R • Alkyl-OH → Aldehyde • Peterson → Enal • Aldehyde azaenolate+Aldehyde • B-Allyl-Ipc+Aldehyde • Aldehyde+B-Allyl (asym) • Carboalumination Alkene • Al-Alkyl → HO-Alkyl • Corey-Fuchs • Fritsch-Buttenberg-Wiechell • O-H → O-SiMe2tBu • Alkene → Diol-1,2 • Diol-1,2 cleavage • Pd/Zn-Alkynyl+Vinyl-X • Alkyne Hydrozirconation • Zr-Vinyl → X-Vinyl • O-SiMe2tBu → O-H • CarboxAcid → CarboxAmide • CarboxAcid → CarboxEster • Li/Br → Li-Vinyl • |
| Reagents: | Alkynyl-ZnX • Vinyl-I • Vinyl-Br • Pd(PPh3)4 • Alkynyl-SiR3 • Vinyl-ZnX • BuLi(tert) • Methacrylate • Vinyl-Br • Carbonate, potassium • Alkynyl-ZnX • PdCl2(PPh3)2 • LiNiPr2 • ZnBr2 • ZnBr2 • Chiral catalyst (Lewis acid) • AlMe3 • O2 • DMSO, (COCl)2 (Swern) • BuLi(sec) • Acetic acid, trifluoro • Chiral auxiliary (boronate) • Crotyl-B(Ipc)2 • SiMe2tBu-Cl • AD-Mix • Periodate, sodium • BuLi(sec) • Acetic acid, trifluoro • BuLi(n) • Chiral catalyst (diamine) • ZrCp2ClH • I2 • PdCl2(PPh3)2 • Alkynyl-ZnX • Vinyl-Zr • Fluoride, R4N+ • NEtiPr2 • Hydroxide, lithium • PPh3=CBr2 • PPh3, CBr4 • |