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Methyl morpholine oxide → Methyl (5r,6s)-rel-13-cyclohexyl-6,7-dihydro-5,6-dihydroxy-5h-indolo[2,1-a][2]benzazepine-10-carboxylate

HRID 860739
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HRID 860739 반응식
[CH:1]1([C:7]2[C:8]3[CH:9]=[CH:10][C:11]([C:25]([O:27][CH3:28])=[O:26])=[CH:12][C:13]=3[N:14]3CC=C[C:17]4[CH:21]=[CH:22][CH:23]=[CH:24][C:16]=4[C:15]=23)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.C[N+]1([O-])CC[O:33]CC1.[CH3:37][C:38]([CH3:40])=[O:39].O>S([O-])([O-])(=O)=S.[Na+].[Na+].O=[Os](=O)(=O)=O>[CH:1]1([C:7]2[C:8]3[CH:9]=[CH:10][C:11]([C:25]([O:27][CH3:28])=[O:26])=[CH:12][C:13]=3[N:14]3[CH2:40][C@H:38]([OH:39])[C@H:37]([OH:33])[C:17]4[CH:21]=[CH:22][CH:23]=[CH:24][C:16]=4[C:15]=23)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1
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반응물 3

HCID 82029Methyl morpholine oxideHCID 11667856methyl 13-cyclohexyl-7H-indolo[2,1-a][2]benzazepine-10-carboxylateHCID 18366337Propan-2-one--water (1/1)

생성물 1

HCID 69207219Methyl (5r,6s)-rel-13-cyclohexyl-6,7-dihydro-5,6-dihydroxy-5h-indolo[2,1-a][2]benzazepine-10-carboxylate수율 91%

시약·촉매·용매 2

HCID 30318
Osmium Tetroxide
촉매
HCID 24477Sodium Thiosulfate용매

실험 절차

OsO4 (23 mg, 0.09 mmol) was added to a stirred solution of methyl 13-cyclohexyl-7H-indolo{2,1-a][2]benzazepine-10-carboxylate (341 mg, 0.92 mmol) and 4-methyl-morpholine N-oxide(430 mg, 3.68 mmol) in acetone-water (50 mL-6 mL) at rt. The reaction mixture was stirred at rt for 18 hr and then diluted with aqueous sodium thiosulfate. The mixture was extracted with ethyl acetate. The organic layer was washed with brine (3×) and dried over sodium sulfate, filtered and evaporated under reduced pressure. The crude product was purified utilizing a Biotage apparatus with a prepacked silica column and using gradients of hexanes:ethyl acetate of from (98:2) to (80:20) to afford the product as a light yellow solid (340 mg, 91%). ESI-MS m/z 406 (MH+); 1H NMR (500 MHz, MeOD) δ 1.25 (m, 1 H) 1.43 (m, 2 H) 1.58 (d, J=13.12 Hz, 1 H) 1.77 (d, J=8.85 Hz, 2 H) 2.02 (m, 4 H) 2.93 (m, 1 H) 3.31 (m, 1 H) 3.93 (s, 3 H) 4.40. (d, J=4.58 Hz, 1 H) 4.52 (m, 1 H) 4.68 (dd, J=14.19, 7.17 Hz, 1 H) 7.40 (t, J=7.32 Hz, 1 H) 7.44 (t, J=7.32 Hz, 1 H) 7.51 (t, J=7.48 Hz, 1 H) 7.70 (d, J=8.55 Hz, 1 H) 7.78 (d, J=7.63 Hz, 1 H) 7.86 (d, J=8.55 Hz, 1 H) 8.15 (s, 1 H).

후처리

  1. extractionThe mixture was extracted with ethyl acetate
  2. washThe organic layer was washed with brine (3×)
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated under reduced pressure
  6. customThe crude product was purified

출처 및 근거

ORD 기록
ord-39ac5afe6e384f05ae655de3decc42b6
출처 데이터셋
uspto-grants-2006_12
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07153848B2

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