Ammonium Chloride → 1-[2-[(4S)-4-(tert-butyldimethyl-silyloxy)-1,2,3,4-tetrahydroquinolin-1-yl]-4-pyridyl]-2,3-bis(methoxycarbonyl)-6,7-dimethoxynaphthalene

HRID 252238ノート

反応式

HRID 252238 の反応式
Br[C:2]1[CH:7]=[C:6]([C:8]2[C:17]3[C:12](=[CH:13][C:14]([O:20][CH3:21])=[C:15]([O:18][CH3:19])[CH:16]=3)[CH:11]=[C:10]([C:22]([O:24][CH3:25])=[O:23])[C:9]=2[C:26]([O:28][CH3:29])=[O:27])[CH:5]=[CH:4][N:3]=1.F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C.[Si:48]([O:55][C@@H:56]1[C:65]2[C:60](=[CH:61][CH:62]=[CH:63][CH:64]=2)[NH:59][CH2:58][CH2:57]1)([C:51]([CH3:54])([CH3:53])[CH3:52])([CH3:50])[CH3:49].CC(C)([O-])C.[Na+].[Cl-].[NH4+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.O.C1(C)C=CC=CC=1>[C:51]([Si:48]([CH3:50])([CH3:49])[O:55][C@@H:56]1[C:65]2[C:60](=[CH:61][CH:62]=[CH:63][CH:64]=2)[N:59]([C:2]2[CH:7]=[C:6]([C:8]3[C:17]4[C:12](=[CH:13][C:14]([O:20][CH3:21])=[C:15]([O:18][CH3:19])[CH:16]=4)[CH:11]=[C:10]([C:22]([O:24][CH3:25])=[O:23])[C:9]=3[C:26]([O:28][CH3:29])=[O:27])[CH:5]=[CH:4][N:3]=2)[CH2:58][CH2:57]1)([CH3:54])([CH3:53])[CH3:52]

参加物

10

反応物 5

HCID 25517Ammonium ChlorideHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 220073291-(2-Bromo-4-pyridyl)-2,3-bis(methoxycarbonyl)-6,7-dimethoxynaphthaleneHCID 23676156Sodium t-butoxideHCID 66866618(4S)-4-(tert-butyldimethylsilyloxy)-1,2,3,4-tetrahydroquinoline

生成物 1

HCID 668676711-[2-[(4S)-4-(tert-butyldimethyl-silyloxy)-1,2,3,4-tetrahydroquinolin-1-yl]-4-pyridyl]-2,3-bis(methoxycarbonyl)-6,7-dimethoxynaphthalene収率 80%

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
100 °C

実験手順

200 mL of a toluene solution containing 20.00 g of 1-(2-bromo-4-pyridyl)-2,3-bis(methoxycarbonyl)-6,7-dimethoxy-naphthalene was sonicated under reduced pressure, then, 975 mg of palladium acetate, 1009 mg of tri-tert-butyl-phosphonium tetrafluoroborate, 13.72 g of (4S)-4-(tert-butyldimethylsilyloxy)-1,2,3,4-tetrahydroquinoline and 6.26 g of sodium tert-butoxide were added to the mixture under room temperature, and after replacing the atmosphere with nitrogen, the mixture was stirred at 100° C. for 4 hours. After cooling the mixture by allowing to stand, 100 mL of a saturated aqueous ammonium chloride solution, 100 mL of water and 100 mL of ethyl acetate were added to the reaction mixture, and said mixture was filtered with Celite. Celite was washed with 100 mL of ethyl acetate, and the organic layer was separated. Said organic layer was washed with 100 g of 20% saline solution, dried over anhydrous magnesium sulfate and then concentrated. The resulting residue was purified by column chromatography on silica gel (n-hexane:ethyl acetate=5:1 to 4:1) to obtain 22.31 g (Yield: 80%) of 1-[2-[(4S)-4-(tert-butyldimethyl-silyloxy)-1,2,3,4-tetrahydroquinolin-1-yl]-4-pyridyl]-2,3-bis(methoxycarbonyl)-6,7-dimethoxynaphthalene.

後処理

  1. customwas sonicated under reduced pressure
  2. temperatureAfter cooling the mixture
  3. filtrationwas filtered with Celite
  4. washCelite was washed with 100 mL of ethyl acetate
  5. customthe organic layer was separated
  6. washwas washed with 100 g of 20% saline solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated
  9. customThe resulting residue was purified by column chromatography on silica gel (n-hexane:ethyl acetate=5:1 to 4:1)

出典と根拠

ORDレコード
ord-21e7e94f16b2428e9efe47328b7ecec8
出典データセット
uspto-grants-2011_01
特許番号
US07868019B2

反応ノート

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