Triphenylphosphine → Ethyl 2-(2-(((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)(tert-butoxycarbonyl)amino)ethoxy)-3-bromo-6-methyl-5-((methylsulfonyl)oxy)benzoate

HRID 577556ノート

反応式

HRID 577556 の反応式
[Br:1][C:2]1[C:3]([OH:19])=[C:4]([C:10]([CH3:18])=[C:11]([O:13][S:14]([CH3:17])(=[O:16])=[O:15])[CH:12]=1)[C:5]([O:7][CH2:8][CH3:9])=[O:6].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:39]([O:46][C:47]1[C:52]([CH2:53][N:54]([CH2:62][CH2:63]O)[C:55](=[O:61])[O:56][C:57]([CH3:60])([CH3:59])[CH3:58])=[C:51]([CH3:65])[CH:50]=[C:49]([CH3:66])[N:48]=1)[C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1.O>[CH2:39]([O:46][C:47]1[C:52]([CH2:53][N:54]([C:55]([O:56][C:57]([CH3:59])([CH3:58])[CH3:60])=[O:61])[CH2:62][CH2:63][O:19][C:3]2[C:2]([Br:1])=[CH:12][C:11]([O:13][S:14]([CH3:17])(=[O:15])=[O:16])=[C:10]([CH3:18])[C:4]=2[C:5]([O:7][CH2:8][CH3:9])=[O:6])=[C:51]([CH3:65])[CH:50]=[C:49]([CH3:66])[N:48]=1)[C:40]1[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=1

参加物

7

反応物 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 86723695Tert-butyl ((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)(2-hydroxyethyl)carbamateHCID 86723782Ethyl 3-bromo-2-hydroxy-6-methyl-5-((methylsulfonyl)oxy)benzoate

生成物 1

HCID 86723783Ethyl 2-(2-(((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)(tert-butoxycarbonyl)amino)ethoxy)-3-bromo-6-methyl-5-((methylsulfonyl)oxy)benzoate収率 53.6%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of ethyl 3-bromo-2-hydroxy-6-methyl-5-((methylsulfonyl)oxy)benzoate (116d, 593 mg, 1.5 mmol), triphenylphosphine (0.50 g, 1.9 mmol), and tert-butyl ((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)(2-hydroxyethyl)carbamate (Cpd LL, 0.54 g, 1.5 mmol) in tetrahydrofuran (12 mL) was cooled to 0° C. then diisopropyl azodicarboxylate (0.40 mL, 1.9 mmol) was added drop wise. The reaction was slowly warmed to room temperature and stirred overnight. The reaction was diluted with water (15 mL) and extracted with ethyl acetate (2×15 mL). The combined organic layers were washed with brine (15 mL), dried over magnesium sulfate, concentrated under vacuum, and purified by column chromatography (20% EtOAc/Heptane) to give ethyl 2-(2-(((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)(tert-butoxycarbonyl)amino)ethoxy)-3-bromo-6-methyl-5-((methylsulfonyl)oxy)benzoate (116e, 0.58 g, 52% yield) as a white solid.

後処理

  1. extractionextracted with ethyl acetate (2×15 mL)
  2. washThe combined organic layers were washed with brine (15 mL)
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated under vacuum
  5. custompurified by column chromatography (20% EtOAc/Heptane)

出典と根拠

ORDレコード
ord-2d94c3680ab24c958277d8ccc03aa2ef
出典データセット
uspto-grants-2015_05
特許番号
US09040515B2

反応ノート

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