Synthesis of a 4,5-epoxy-2-cyclohexen-1-one derivative via epoxide ring opening, 1,3-carbonyl transposition and epoxide ring regeneration: a synthetic study on a scyphostatin analogue.
A 6-alkyl-4,5-epoxy-6-hydroxy-2-cyclohexen-1-one derivative, a model compound for the hydrophilic moiety of scyphostatin, was stereoselectively synthesized from the Diels-Alder adduct. The key steps were the reductive cleavage of the 4,5-epoxide ring of the epoxidated adduct, the 1,3-carbonyl transposition of the 3-carbonyl group to the C1 position by a Wharton reaction and stereoselective bromination to provide a trans bromohydrin derivative, a precursor to the desired compound. Desilylation of the bromohydrin derivative with TBAF directly gave the target compound.
Takagi
Ryukichi
R
Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, 739-8526, Japan.
Tojo
Kengo
K
Iwata
Masato
M
Ohkata
Katsuo
K
D000577:Amides / Q000138:chemical synthesis*; D003510:Cyclohexanes / Q000138:chemical synthesis* / Q000737:chemistry; D004852:Epoxy Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D011753:Pyrones / Q000138:chemical synthesis*; D021241:Spectrometry, Mass, Electrospray Ionization; D017550:Spectroscopy, Fourier Transform Infrared
C511685:4,5-epoxy-2-cyclohexen-1-one; D000577:Amides; D003510:Cyclohexanes; D004852:Epoxy Compounds; D011753:Pyrones; C121123:scyphostatin