Total synthesis of Brasilenyne:
| Reference: | Denmark, S.; Yang, S. M. J. Am. Chem. Soc. 2004, 126, 12432. DOI |
| Reactions: | Lactone-5 • O-H → O-PMB • CarboxAmide(Weinreb) → Aldehyde • O-H → O-SiMe2tBu • O-PMB → O-H • Alkyl-OH → Alkyl-Cl • Appel → Cl • Diimide+Alkyne • Alkyne → Vinyl-I • Peterson → Enyne • Li-Allenyl/Propargyl+Aldehyde • Aldehyde+Li-Silane • Si-Alkynyl+Acetal • Acetal+Si-R • Lactone-5 • B-Allyl-Ipc+Aldehyde • Aldehyde+B-Allyl (asym) • RCM → Ring-Si • Pd/Si-Vinyl+Vinyl-X • Ether-9+ • Si-Alkynyl → I-Alkynyl • CarboxAcid → Alkyl-OH • CompRed-CarboxAcid/CarboxEster+M-H • CarboxEster → CarboxAmide(Weinreb) • O-H → O-SiMe2tBu • Si-Alkynyl → H-Alkynyl • Alkyl-OH → Aldehyde • O-SiMe2tBu → O-H • |
| Reagents: | BF3·OEt2 • BH3·THF • SiMe2tBu-Cl • Alkynyl-SiR3 • TiCl4 • TsOH • Alkynyl-SiR3 • Alkynyl-I • NIS • Acetic acid • Vinyl-I • NMe(OMe)-AlMe2 • Ag2O • AlHiBu2 • Allyl-B(Ipc)2 • BF3 • BF3 • NEt3 • Schrock cat • PdCl(Allyl) • Fluoride, R4N+ • SiMe2tBu-OTf • DDQ • Dess-Martin • Allenyl-Li • Alkynyl-SiR3 • Fluoride, R4N+ • PBu3, CCl4 • Chiral auxiliary (boronate) • Diimide • |