Total synthesis of Dictyoxetane New:
| Reference: | Hugelshofer, C.L.; Magauer, T. J. Am. Chem. Soc. 2016, 138, 6420-6423. DOI |
| Reactions: | O-SiMe2tBu → O-H • Robinson annulation, ketone • Aldol-Na → Enone • Cyclohexenone • Bicyclo(430) • Enone → Ketal • Alkene isomerization • Alkene → Diol-1,2 • Pinacol • Mg-Alkyl+Ketone • Mg-R → Ce-R • O-H → O-Bn • Williamson etherification • Ketal → Ketone • Aldol-Li → Aldol • O-H → O-SiMe2tBu • Mg-Vinyl+Ketone • Mg-R → La-R • Alkyl-OH → Ketone • Mg-Alkyl+Ketone • Mg-R → La-R • RCM → Ring-C • Cycloheptane • Bicyclo(540) • O-H → O-SiMe3 • CompNu-O-H/O-H+R3Si-X • O-OH → O-H • Allylic oxidation → Allyl-OH • Singlet oxygen+Alkene • O-H → O-SO2Me • O-H → O-Alkyl • Williamson etherification • Ether-4 • Iodoetherification • Ether-5 • Bicyclo(321)-oxa • Bicyclo(320)-oxa • O-Bn → O-H • Alkyl-X → Alkyl-H • |
| Reagents: | H2SO4 • Hydroxide, potassium • Glycol • OsO4, NMO • PPh3 • Cl2 • Alkyl-MgX • Benzyl-X • HCl, H2O • KN(SiMe3)2 • LiNiPr2 • Acetaldehyde • CeCl3 • SiMe2tBu-Cl • Imidazole • DMAP • Propenyl-MgX • LaCl3 • Fluoride, R4N+ • RuO4-Pr4N+, NMO • LaCl3 • Quinone • SiMe3-I • O2 (singlet) • Photochemistry • PPh3 • Sulfonyl chloride, methane, NEt3 • NaH • NIS • H2, Pd • |