Total synthesis of Spongistatin 2 - (Part 4) (Smith) New:
| Reference: | Smith, A. B., III; Lin, Q.; Doughty, V. A.; Zhuang, L; McBriar, M. D.; Kerns, J. K.; Brook, C. S.; Murase, N.; Nakayama, K. Angew. Chem. Int. Ed. 2001, 40, 196. DOI-1 DOI-2 (Part 1) (Part 2) (Part 3) (Part 5) (Part 6) (Part 7) |
| Reactions: | B-Allyl-Ipc+Aldehyde • Aldehyde+B-Allyl (asym) • O-SiPh2tBu → O-H • O-H → O-Bn • Sharpless epoxidation • O-H → O-C(O)R • Epoxide → Diol • Oxymercuration Alkene • Ether-6 • Alkyl-Hg → Alkyl-OH • O-C(O)R → O-H • Diol-1,3 → Ketal • Alkyl-OH → Aldehyde • Aldehyde epimerization • O-H → O-Boc • B-Allyl-Ipc+Aldehyde • Aldehyde+B-Allyl (asym) • Iodolactonization • Li/H → Li-Dithiane • Li-Dithiane+Epoxide • Li-Dithiane+Aldehyde • Aldehyde+Li-Sulfide • Iodohydrin → Epoxide • Diol-1,3 → Ketal • Ketal(thio) → Ketone • Ketone → Ketal(Me) • Ether-6 • O-H → O-SiMe2tBu • CompNu-O-H/O-H+R3Si-X • O-Bn → O-H • O-H → O-SiPh2tBu • CompNu-O-H/O-H+R3Si-X • O-H → O-SiEt3 • O-Piv → O-H • O-C(O)R → O-H • Alkyl-OH → Alkyl-I • O-H → O-Piv • CompNu-O-H/O-H+RC(O)X • |
| Reagents: | Crotyl-B(Ipc)2 • BF3·OEt2 • H2O2, NaOH • Chiral auxiliary (boronate) • Benzyl-X • Fluoride, R4N+ • Tartrate, diethyl • Ti(OiPr)4 • Hydroperoxide, tbutyl • Ti(OiPr)4 • Hg(OAc)2 • Acetic anhydride, NEt3 • O2 • BH4-Na+ • Hydroxide, sodium • Acetone (solvent) • TsOH • DMSO, (COCl)2 (Swern) • NEt3 • Crotyl-B(Ipc)2 • BF3·OEt2 • H2O2, NaOH • Boc2O • IBr • Chiral auxiliary (boronate) • NaN(SiMe3)2 • Epoxide • BuLi(n) • Me2C(OMe)2 • Carbonate, potassium • Sulfonic acid, Camphor • Lutidine • HOMe (react) • Piv-Cl • DMAP • SiMe2tBu-OTf • Lutidine • Pd/C • SiPh2tBu-Cl • SiEt3-OTf • AlHiBu2 • I2 • |