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

反応式

HRID 513357 の反応式
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]

参加物

8

反応物 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

生成物 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)methanone収率 70%

試薬・触媒・溶媒 3

HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
25 °C

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-cfcd74d726c74eb38d09f8c8a8256876
出典データセット
uspto-grants-2015_08
特許番号
US09102704B2

関連ノート

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