Allylic oxidation of 1-methyl-1-cycloheptene

Oxidation of the Meroterpenoid (−)-Terreumol C from the Mushroom Tricholoma terreum: Discovery of Cytotoxic Analogues

“…9 The oxygenation pattern of terreumol D (4), carrying a hydroxy group at C8, was not observed, although there are a few known cases where SeO 2 -mediated oxidation occurs at the less substituted side of a trisubstituted double bond, albeit only as a side reaction. 10 Treatment of 5 with catalytic amounts of Pd(OAc) 2 (0.1 equiv) in the presence of p-benzoquinone (2 equiv) in acetic acid 11 afforded the TBS-protected bis(acetoxy) compound, which was desilylated to afford the masked aldehyde 9 (51% over two steps). Geminal bisacetoxylation in the allylic position is unprecedented.…”

“…It is known that SeO 2 -mediated oxidation occurs at the higher substituted side in trisubstituted olefins, with a preference for CH 2 rather than CH 3 groups and for endo- rather than exocyclic positions . The oxygenation pattern of terreumol D ( 4 ), carrying a hydroxy group at C8, was not observed, although there are a few known cases where SeO 2 -mediated oxidation occurs at the less substituted side of a trisubstituted double bond, albeit only as a side reaction …”

“…(1aR,11aS,E)-7,10-Bis((tert-butyldimethylsilyl)oxy)-8-methoxy-1a-methyl-5-((phenylselanyl)methyl)-1a,3,6,11atetrahydrobenzo [4,5]cyclodeca[1,2-b]oxiren-11(2H)-one (10). AgOAc (21.9 mg, 131.364 μmol) and PhSeBr (8.9 mg, 37.533 μmol) were added to a solution of bicycle 5 (10 mg, 18.766 μmol) in AcOH (1 mL).…”