Ethyl Acetate → (S,E)-(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrol-1-yl)(5-methoxy-2-nitro-4-(triisopropylsilyloxy)phenyl)methanone

HRID 513357

반응식

HRID 513357 반응식
FC(F)(F)S(O[C:7]1[CH2:11][C@@H:10]([CH2:12][O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15])[N:9]([C:21](=[O:44])[C:22]2[CH:27]=[C:26]([O:28][CH3:29])[C:25]([O:30][Si:31]([CH:38]([CH3:40])[CH3:39])([CH:35]([CH3:37])[CH3:36])[CH:32]([CH3:34])[CH3:33])=[CH:24][C:23]=2[N+:41]([O-:43])=[O:42])[CH:8]=1)(=O)=O.[CH:47](/B(O)O)=[CH:48]\[CH3:49].P([O-])([O-])([O-])=O.[K+].[K+].[K+].C(OCC)(=O)C>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[Si:14]([O:13][CH2:12][C@@H:10]1[CH2:11][C:7](/[CH:47]=[CH:48]/[CH3:49])=[CH:8][N:9]1[C:21]([C:22]1[CH:27]=[C:26]([O:28][CH3:29])[C:25]([O:30][Si:31]([CH:32]([CH3:34])[CH3:33])([CH:38]([CH3:39])[CH3:40])[CH:35]([CH3:36])[CH3:37])=[CH:24][C:23]=1[N+:41]([O-:43])=[O:42])=[O:44])([C:17]([CH3:18])([CH3:19])[CH3:20])([CH3:16])[CH3:15]

참가 물질

8

반응물 4

HCID 8857Ethyl AcetateHCID 62657Potassium Phosphate, TribasicHCID 6157276((1E)-prop-1-en-1-yl)boronic acidHCID 71550534(S)-5-((tert-butyldimethylsilyloxy)methyl)-1-(5-methoxy-2-nitro-4-(triisopropylsilyloxy)benzoyl)-4,5-dihydro-1H-pyrrol-3-yl trifluoromethanesulfonate

생성물 1

HCID 86717761(S,E)-(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrol-1-yl)(5-methoxy-2-nitro-4-(triisopropylsilyloxy)phenyl)methanone수율 70%

시약·촉매·용매 3

HCID 178418397HCID 178418397, 화합물촉매HCID 962Water용매HCID 312751,4-Dioxane용매

반응 조건

온도
25 °C

실험 절차

Tetrakis(triphenylphosphine)palladium(0) (0.41 g, 0.35 mmol, 0.03 eq) was added to a mixture of the triflate 5 (8.4 g, 11.8 mmol, 1.0 eq), E-1-propene-1-ylboronic acid (1.42 g, 16.5 mmol, 1.4 eq) and potassium phosphate (5.0 g, 23.6 mmol, 2.0 eq) in dry dioxane (60 mL) under a nitrogen atmosphere. The mixture was stirred at 25° C. for 120 mins when LC/MS indicated complete reaction. Ethyl acetate (120 mL) and water (120 mL) were added, the organic phase was removed, washed with brine (20 mL), dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, 95/5 v/v n-hexane/EtOAc to 90/10 v/v n-hexane/EtOAc) to afford the product as a yellow foam (4.96 g, 70%). LC/MS (4.477 min (ES+)), m/z: 605.0 [M+H]+. 1H NMR (400 MHz, CDCl3) δ 7.67 (s, 1H), 6.74 (s, 1H), 5.93 (d, 1H, J=15.4 Hz), 5.67 (s, 1H), 4.65 (m, 1H), 4.04 (m, 2H), 3.86 (s, 3H), 2.85 (m, 1H), 2.71 (m, 1H), 1.72 (dd, 3H, J=6.8, 1.0 Hz), 1.30-1.22 (m, 3H), 1.07 (d, 18H, J=7.2 Hz), 0.87 (s, 9H), 0.08 (s, 3H), 0.07 (s, 3H).

후처리

  1. customreaction
  2. customthe organic phase was removed
  3. washwashed with brine (20 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by flash chromatography (silica gel, 95/5 v/v n-hexane/EtOAc to 90/10 v/v n-hexane/EtOAc)

출처 및 근거

ORD 기록
ord-cfcd74d726c74eb38d09f8c8a8256876
출처 데이터셋
uspto-grants-2015_08
특허 번호
US09102704B2

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