Total synthesis of Kallilolide B New:
| Reference: | Marshall, J. A.; Wallace, E. M.; Coan, P. S. J. Org. Chem. 1995, 60, 796-797. DOI |
| Reactions: | Allene epimerization • Aldehyde → Alkyl-OH • Wittig-methoxymethyl • EnoateEster → Allyl-OH • Claisen-Johnson • CarboxEster → Alkyl-OH • EnoateEster → Allyl-OH • Sn-Allenyl+Aldehyde • Aldehyde+Sn-R • Allene synthesis • Allyl-OH → Enone • Furan synthesis • Li-Aryl+CarboxAmide • Li/H → Li-Furyl • Li/H → Li-Allenyl/propargyl • 2,3-Sigmatropic Anionic • O-H → O-SO2Me • Pd-Carboxylation • Allene synthesis • Cyclododecane • CarboxEster → CarboxAcid • Lactone-5 • O-H → O-Alkyl • Williamson etherification • Ether-9+ • Propargyl-OH → Propargyl-Cl • CarboxEster → Alkyl-OH • HWE → EnoateEster-cis • O-SiMe2tBu → O-H • |
| Reagents: | DMSO, (COCl)2 (Swern) • PPh3=C(Me)-CO2R • AlHiBu2 • AlHiBu2 • Oxalyl chloride • Propargyl-Br • SnCl2 • Iodide, sodium • BuLi(n) • Formaldehyde • SiMe2tBu-Cl • NEt3 • DMSO, (COCl)2 (Swern) • NEt3 • AgNO3 • Fluoride, R4N+ • BuLi(tert) • DMF (react) • P(O)(OCH2CF3)2CH2-C(O)OMe • 18-crown-6 • KN(SiMe3)2 • Sulfonyl chloride, methane • Chloride, lithium • Lutidine • AlHiBu2 • NaH • 18-crown-6 • BuLi(n) • Sulfonyl chloride, methane, NEt3 • Pd2(dba)3 • PPh3 • CO • PPh3 • Fluoride, R4N+ • |