Sodium Bicarbonate → tert-butyl (2S)-2-{[tert-butyl(dimethyl)silyl]oxy}-3-phenoxypropyl{[(2S)-6-(2,2-dimethyl-4-oxo-4H-1,3-benzodioxin-7-yl)-3,4-dihydro-2H-chromen-2-yl]methyl}carbamate

HRID 47693ノート

反応式

HRID 47693 の反応式
[Si:1]([O:8][C@H:9]([CH2:39][O:40][C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[CH2:10][N:11]([CH2:19][C@@H:20]1[CH2:29][CH2:28][C:27]2[C:22](=[CH:23][CH:24]=[C:25](B3OC(C)(C)C(C)(C)O3)[CH:26]=2)[O:21]1)[C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].FC(F)(F)S(O[C:53]1[CH:54]=[CH:55][C:56]2[C:61](=[O:62])[O:60][C:59]([CH3:64])([CH3:63])[O:58][C:57]=2[CH:65]=1)(=O)=O.C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C(Cl)Cl.Cl[Pd]Cl.[Fe]>[Si:1]([O:8][C@H:9]([CH2:39][O:40][C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[CH2:10][N:11]([CH2:19][C@@H:20]1[CH2:29][CH2:28][C:27]2[C:22](=[CH:23][CH:24]=[C:25]([C:53]3[CH:54]=[CH:55][C:56]4[C:61](=[O:62])[O:60][C:59]([CH3:64])([CH3:63])[O:58][C:57]=4[CH:65]=3)[CH:26]=2)[O:21]1)[C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

参加物

6

反応物 3

HCID 516892Sodium BicarbonateHCID 22351418HCID 22351418、化合物HCID 86587741tert-butyl (2S)-2-{[tert-butyl(dimethyl)silyl]oxy}-3-phenoxypropyl{[(2S)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydro-2H-chromen-2-yl]methyl}carbamate

生成物 1

HCID 86587740tert-butyl (2S)-2-{[tert-butyl(dimethyl)silyl]oxy}-3-phenoxypropyl{[(2S)-6-(2,2-dimethyl-4-oxo-4H-1,3-benzodioxin-7-yl)-3,4-dihydro-2H-chromen-2-yl]methyl}carbamate収率 76%

試薬・触媒・溶媒 2

HCID 53485975CID 53485975触媒HCID 1140Toluene溶媒

反応条件

温度
80 °C

実験手順

To a degassed solution of tert-butyl (2S)-2-{[tert-butyl(dimethyl)silyl]oxy}-3-phenoxypropyl{[(2S)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydro-2H-chromen-2-yl]methyl}carbamate (1.0 g, 1.53 mmol, 1.0 eq.) in toluene (12 mL) were added 2,2-dimethyl-4-oxo-4H-1,3-benzodioxin-7-yl trifluoromethanesulfonate (0.60 g, 1.84 mmol, 1.2 equiv.), dichloro[1,1′-bis(diphenylphosphino)ferrocene] palladium(II) dichloromethane adduct (0.18 g, 0.23 mmol, 0.15 eq.) and saturated sodium bicarbonate (8.0 mL) under argon atmosphere at room temperature. The reaction mixture was allowed to heat up at 80° C. under argon atmosphere for 18 hours. The mixture was then quenched with distilled water (10 mL) and extracted with ethyl acetate (3×10 mL). The combined extracts were washed with brine (20 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure to afford black oil. Purification by flash chromatography on a silica gel column (5%-15% ethyl acetate/hexanes) yielded the desired product as colorless oil (0.81 g, 76%). 1H NMR (CDCl3) δ7.86 (d, 1 H), 7.27-6.78 (m, 11H), 4.20-3.85 (m, 2H), 3.81-3.40 (m, 4H), 3.37-3.20 (m, 2H), 2.80-2.21 (m, 2H), 1.95-1.84 (m, 1H), 1.64 (s, 7H), 1.39 (s, 9H), 0.81 (s, 9H), 0.020 (s, 6H).

後処理

  1. customThe mixture was then quenched with distilled water (10 mL)
  2. extractionextracted with ethyl acetate (3×10 mL)
  3. washThe combined extracts were washed with brine (20 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customto afford black oil
  8. customPurification by flash chromatography on a silica gel column (5%-15% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-687b92fbaa4944b9bdbcd8445fb7d6da
出典データセット
uspto-grants-2004_03
特許番号
US06699860B2

反応ノート

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