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 407119노트

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HRID 407119 반응식
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+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.O>[Si:48]([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)([C:51]([CH3:54])([CH3:53])[CH3:52])([CH3:50])[CH3:49]

참가 물질

10

반응물 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

생성물 1

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

시약·촉매·용매 4

HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 1140Toluene용매HCID 8857Ethyl Acetate용매

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온도
100 °C

실험 절차

A solution of 20.00 g of 1-(2-bromo-4-pyridyl)-2,3-bis(methoxycarbonyl)-6,7-dimethoxynaphthalene in 200 mL of toluene was sonicated under reduced pressure, and then to the solution were added 975 mg of palladium acetate, 1009 mg of tri-tert-butylphosphonium tetrafluoroborate, 13.72 g of (4S)-4-(tert-butyldimethylsilyloxy)-1,2,3,4-tetrahydroquinoline and 6.26 g of sodium tert-butoxide at room temperature. After nitrogen substitution, the mixture was stirred at 100° C. for 4 hours. After radiation, to the reaction solution were added 100 mL of saturated aqueous ammonium chloride solution, 100 mL of water and 100 mL of ethyl acetate, and the mixture was filtered through Celite®. Celite® was washed with 100 mL of ethyl acetate, and then the organic layer was separated. The organic layer was washed with 100 g of 20% saline, dried over magnesium sulfate, and then concentrated. The resulting residue was purified by column chromatography on silica gel (n-hexan/ethyl acetate=5/1 to 4/1) to give 22.31 g of 1-[2-[(4S)-4-(tert-butyldimethylsilyloxy)-1,2,3,4-tetrahydroquinolin-1-yl]-4-pyridyl]-2,3-bis(methoxycarbonyl)-6,7-dimethoxynaphthalene (yield: 80%).

후처리

  1. filtrationthe mixture was filtered through Celite®
  2. washCelite® was washed with 100 mL of ethyl acetate
  3. customthe organic layer was separated
  4. washThe organic layer was washed with 100 g of 20% saline
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated
  7. customThe resulting residue was purified by column chromatography on silica gel (n-hexan/ethyl acetate=5/1 to 4/1)

출처 및 근거

ORD 기록
ord-9eeaa7a1c1fc4f50bff5b555ad949f3c
출처 데이터셋
uspto-grants-2014_06
특허 번호
US08754221B2

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