Total synthesis of Pleuromutilin (Reisman):
| Reference: | Farney, E. P.; Feng, S. S.; Schafers, F.; Reisman, S. E. J. Am. Chem. Soc. 2018, 140, 1267-1270. DOI |
| Reactions: | Kornblum oxidation • Allyl-X → Allyl-I • Hydrogen atom transfer reduction • ConjAdd M-SR • YnoateEster+Thiolate • Cu-Me+EnoateEster • ConjAdd-Elimination • ConjAdd Cu-Me • Mg-R → Cu-R • CarboxEster → Alkyl-OH • Allyl-OH → Allyl-B • ConjAdd-Silylation • Enone+Cu-R • Cu-Alkyl+Enone • ConjAdd Cu-Alkyl • Mg-R → Cu-R • Saegusa oxidation • Ketone → Enone • ConjAdd Cu-Vinyl • Cu-Vinyl+Enone • Mg-R → Cu-R • Allylic oxidation → Allyl-Cl • Acetal → Aldehyde • Aldol-Acid → Enone • Cyclopentene • Bicyclo(430) • Mg-Alkyl+Ketone • CompE+-Ketone/Allyl-X+M-R • Allyl-OH → Enone (rearr) • B-Allyl+Aldehyde • O-H → O-MOM • O-CPh3 → O-H • Alkyl-OH → Aldehyde • Ketyl+Enone • Cyclooctane • Bicyclo(531) • Ketone → EnolSilane • Alkene → Alkane • Ketone → Alkyl-OH • O-H → O-C(O)R • O-C(O)R → O-H • O-MOM → O-H • EnolSilane → Ketone • Ozonolysis • Pd/B-B+HO-Allyl • |
| Reagents: | DMSO (solvent) • Thiolate, phenyl • NaOMe • Me-MgBr • CuI • AlHiBu2 • B2(OH)4 • Pd(BF4)2(MeCN)4 • Alkyl-MgX • SiMe3-Cl • Pd(OAc)2 • O2 • CuI • CuI • Cyanuric chloride • HCl, H2O • Me-MgCl • CeCl3 • CrO3Cl·PyH (PCC) • Iodide, sodium • Formic acid • CuOTf • NIS • SmI2 • SiMe3-Cl • LiN(SiMe3)2 • SiiPr3-OTf • HSiPhH2 • Hydroperoxide, tbutyl • Li°/NH3 • Carbodiimide • NEt3 • HCl • DMAP • Chiral auxiliary (boronate) • O3 • Cu(OAc)2 • |