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Cesium fluoride → Methyl 1-((3-fluoro-4-(5-(1-(4-fluorophenyl)vinyl)thiazolo[5,4-b]pyridine-2-yl)phenyl)methyl)azetidine-3-carboxylate

HRID 1177499
ノート
印刷プレビュー

反応式

HRID 1177499 の反応式
[F-].[Cs+].Cl[C:4]1[N:9]=[C:8]2[S:10][C:11]([C:13]3[CH:18]=[CH:17][C:16]([CH2:19][N:20]4[CH2:23][CH:22]([C:24]([O:26][CH3:27])=[O:25])[CH2:21]4)=[CH:15][C:14]=3[F:28])=[N:12][C:7]2=[CH:6][CH:5]=1.C([Sn](CCCC)(CCCC)[C:34]([C:36]1[CH:41]=[CH:40][C:39]([F:42])=[CH:38][CH:37]=1)=[CH2:35])CCC>CN(C=O)C.CCOC(C)=O.[Cu]I.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:28][C:14]1[CH:15]=[C:16]([CH2:19][N:20]2[CH2:23][CH:22]([C:24]([O:26][CH3:27])=[O:25])[CH2:21]2)[CH:17]=[CH:18][C:13]=1[C:11]1[S:10][C:8]2[C:7]([N:12]=1)=[CH:6][CH:5]=[C:4]([C:34]([C:36]1[CH:41]=[CH:40][C:39]([F:42])=[CH:38][CH:37]=1)=[CH2:35])[N:9]=2
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 3

HCID 25953Cesium fluorideHCID 67111781Tributyl(1-(4-fluorophenyl)vinyl)stannaneHCID 86638707Methyl 1-((4-(5-chlorothiazolo[5,4-b]pyridine-2-yl)-3-fluorophenyl)methyl)azetidine-3-carboxylate

生成物 1

HCID 67111924Methyl 1-((3-fluoro-4-(5-(1-(4-fluorophenyl)vinyl)thiazolo[5,4-b]pyridine-2-yl)phenyl)methyl)azetidine-3-carboxylate

試薬・触媒・溶媒 4

HCID 24350
Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)
触媒
HCID 11979704Tetrakis(triphenylphosphine)palladium触媒
HCID 6228Dimethylformamide溶媒
HCID 8857Ethyl Acetate溶媒

反応条件

温度
45 °C

実験手順

A slurry of cesium fluoride (0.310 g, 2.04 mmol), copper(I) iodide (0.0194 g, 0.102 mmol), tetrakis(triphenylphosphine) palladium (0) (0.0590 g, 0.0510 mmol), methyl 1-((4-(5-chlorothiazolo[5,4-b]pyridine-2-yl)-3-fluorophenyl)methyl)azetidine-3-carboxylate (0.400 g, 1.02 mmol), tributyl(1-(4-fluorophenyl)-vinyl)stannane (0.504 g, 1.22 mmol) in 2 mL DMF was sealed and heated to 45° C. overnight. The reaction mixture became purple/black and was allowed to stir at ambient temperature for 24 h. The reaction mixture was diluted with EtOAc and filtered through celite, then the filtrate was washed with water. The water layer was removed, and the EA layer was treated with DCM until only slightly cloudy, the organics were dried over magnesium sulfate, filtered, and concentrated in vacuo. The resulting material was purified by silica gel chromatography, 0-100% EA/hexanes to give methyl 1-((3-fluoro-4-(5-(1-(4-fluorophenyl)vinyl)thiazolo[5,4-b]pyridine-2-yl)phenyl)methyl)azetidine-3-carboxylate as an orange solid. MS (ESI) m/z: calculated: 477.1; Observed: 478.1 (M++1).

後処理

  1. filtrationfiltered through celite
  2. washthe filtrate was washed with water
  3. customThe water layer was removed
  4. additionthe EA layer was treated with DCM until only slightly cloudy
  5. dry with materialthe organics were dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe resulting material was purified by silica gel chromatography, 0-100% EA/hexanes

出典と根拠

ORDレコード
ord-4b550b3540214eb38ef70e8d35dee4e0
出典データセット
uspto-grants-2010_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07842685B2

反応ノート

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