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Triethylamine → (4R,5R)-5-Phenyl-4-(2-(pyridin-2-ylethynyl)pyridin-4-yl)oxazolidin-2-one

HRID 2362443
ノート
印刷プレビュー

反応式

HRID 2362443 の反応式
Br[C:2]1[CH:7]=[C:6]([C@@H:8]2[C@@H:12]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[O:11][C:10](=[O:19])[NH:9]2)[CH:5]=[CH:4][N:3]=1.C[Si]([C:24]#[C:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=1)(C)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>CN(C)C=O.C(OCC)(=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:13]1([C@H:12]2[O:11][C:10](=[O:19])[NH:9][C@@H:8]2[C:6]2[CH:5]=[CH:4][N:3]=[C:2]([C:24]#[C:25][C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=3)[CH:7]=2)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

10

反応物 5

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 5228592-(Trimethylsilylethynyl)pyridineHCID 2724141Tetrabutylammonium FluorideHCID 86673413(4R,5R)-4-(2-Bromopyridin-4-yl)-5-phenyloxazolidin-2-one

生成物 1

HCID 69084771(4R,5R)-5-Phenyl-4-(2-(pyridin-2-ylethynyl)pyridin-4-yl)oxazolidin-2-one

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A solution of (4R,5R)-4-(2-bromopyridin-4-yl)-5-phenyloxazolidin-2-one (20 mg, 0.063 mmol) and 2-((trimethylsilyl)ethynyl)pyridine (10.99 mg, 0.063 mmol) in dimethylformamide (300 mL) was purged with nitrogen for 30 min. The reaction was treated with triphenylphosphine (4.93 mg, 0.019 mmol), and purged 10 minutes longer. To this was added PdCl2(PPh3)2 (2.199 mg, 3.13 mmol) and copper(I) iodide (1.193 mg, 6.27 mmol). After purging 10 min longer, the reaction was treated with triethylamine (13.1 mL, 0.094 mmol) and placed in an 85° C. oil bath. To this was added tetrabutylammonium fluoride (1M in tetrahydrofuran, 68.9 mL, 0.069 mmol) dropwise. The reaction was stirred at this temperature for 1 h. The reaction was cooled to room temperature, diluted with ethyl acetate, washed with water, then brine, dried over magnesium sulfate, and concentrated. Column chromatography (50%-->100% EtOAc/Hex) gave 19 mg (89%) as a foam solid. 1H-NMR (CDCl3, 500 MHz) δ 8.68 (d, J=4.6, 1H), 8.60 (d, J=5.2, 1H), 7.73 (ddd, J=7.9, 7.6, 1.6, 1H), 7.59 (d, J=7.6, 1H), 7.38-7.50 (m, 5H), 7.33 (m, 3H), 7.25 (m, 1H), 5.19 (d, J=7.3, 1H), 4.88 (d, J=7.3, 1H). 13C-NMR (CDCl3, 126 MHz) δ 158.8, 151.0, 150.3, 148.6, 143.3, 142.1, 136.7, 136.6, 129.6, 129.3, 127.9, 126.2, 125.1, 123.9, 120.9, 88.5, 87.4, 85.2, 63.6. Mass spec.: 342.0 (MH)+.

後処理

  1. custompurged 10 minutes longer
  2. customAfter purging 10 min longer
  3. customplaced in an 85° C.
  4. washwashed with water
  5. dry with materialbrine, dried over magnesium sulfate
  6. concentrationconcentrated
  7. customColumn chromatography (50%-->100% EtOAc/Hex) gave 19 mg (89%) as a foam solid

出典と根拠

ORDレコード
ord-d4ce31934bce4655aad72bda7faddebd
出典データセット
uspto-grants-2014_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08691821B2

反応ノート

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