tert-Butyl hydroperoxide → HCID 10973444, compound

HRID 1779705Notes

Reaction equation

C([O:5]O)(C)(C)C.[C:7]([O:11][C:12]([NH:14][C@@H:15]1[C@@H:20]([C:21]2[C:22]([C:38]([O:40][CH3:41])=[O:39])=[C:23]([O:30][CH2:31][C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)[C:24]3[O:28][CH2:27][O:26][C:25]=3[CH:29]=2)[CH:19]=[CH:18][C@@H:17]([OH:42])[C@H:16]1[OH:43])=[O:13])([CH3:10])([CH3:9])[CH3:8]>CCCCCCCCCC.C1C=CC=CC=1.C/C(/O)=C\C(C)=O.C/C(/O)=C\C(C)=O.O=[V]>[C:7]([O:11][C:12]([NH:14][C@H:15]1[C@H:16]([OH:43])[C@H:17]([OH:42])[C@@H:18]2[O:5][C@@H:19]2[C@@H:20]1[C:21]1[C:22]([C:38]([O:40][CH3:41])=[O:39])=[C:23]([O:30][CH2:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:24]2[O:28][CH2:27][O:26][C:25]=2[CH:29]=1)=[O:13])([CH3:10])([CH3:8])[CH3:9]

Participants

Conditions

Temperature: 60 °C

Procedure

t-Butylhydroperoxide in decane (5M, 0.45 ml) was added to a solution of methyl 6-[(1R,4R,5S,6R)-6-(tert-butyloxycarbonylamino)-4,5-dihydroxy-2-cyclohexen-1-yl]-4-(phenylmethoxy)-1,3-benzodioxole-5-carboxylate (280 mg, 0.55 mmol) and vanadyl acetylacetonate (7 mg, 0.026 mmol) in benzene (10 ml). After stirring for 2 h at 60° C, the reaction mixture was concentrated under reduced pressure and subjected to chromatography (hexane/ethyl acetate, 1:5) to afford 129 mg (53%) of epoxide 16 and 42 mg of recovered starting material. 1H NMR (270 MHz, CDCl3) ε 7.27~7.40 (m, 5H), 7.04 (s, 1H), 5.99 (d, J=2.3 Hz, 2H), 5.68 (bd, J=7.3 Hz, 1H), 5.24 (AB, J=11.3 Hz, Δν=16.5 Hz, 2H), 4.28 (t, J=4.99 Hz, 1H), 3.83 (m, 4H), 3.35~3.46 (m, 3H), 3.07 (d, J=10.9 Hz, 1H), 1.33 (s, 9H).

Workup

concentrationthe reaction mixture was concentrated under reduced pressure

Sources & evidence

ORD record: ord-f7d4fc920ff4452a949b19c962cb22d7
Source dataset: uspto-grants-1997_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05627280

Reaction notes

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