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Cesium carbonate → 3-(2-Fluoro-4-trimethylsilanyl-phenylamino)-1-(2-triisopropylsilanyloxy-ethyl)-1H-pyrrolo[3,2-c]pyridine-2-carboxylic acid methyl ester

HRID 2264916
ノート
印刷プレビュー

反応式

HRID 2264916 の反応式
[CH3:1][O:2][C:3]([C:5]1[N:13]([CH2:14][CH2:15][O:16][Si:17]([CH:24]([CH3:26])[CH3:25])([CH:21]([CH3:23])[CH3:22])[CH:18]([CH3:20])[CH3:19])[C:12]2[CH:11]=[CH:10][N:9]=[CH:8][C:7]=2[C:6]=1[NH2:27])=[O:4].[F:28][C:29]1[CH:34]=[C:33]([Si:35]([CH3:38])([CH3:37])[CH3:36])[CH:32]=[CH:31][C:30]=1OS(C(F)(F)F)(=O)=O.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.CCOC(C)=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:1][O:2][C:3]([C:5]1[N:13]([CH2:14][CH2:15][O:16][Si:17]([CH:24]([CH3:26])[CH3:25])([CH:18]([CH3:20])[CH3:19])[CH:21]([CH3:23])[CH3:22])[C:12]2[CH:11]=[CH:10][N:9]=[CH:8][C:7]=2[C:6]=1[NH:27][C:30]1[CH:31]=[CH:32][C:33]([Si:35]([CH3:37])([CH3:36])[CH3:38])=[CH:34][C:29]=1[F:28])=[O:4]
参加物実験手順後処理出典と根拠反応ノート

参加物

8

反応物 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 59596436Trifluoromethanesulfonic acid 2-fluoro-4-trimethylsilanyl-phenyl esterHCID 595966513-Amino-1-(2-triisopropylsilanyloxy-ethyl)-1H-pyrrolo[3,2-c]pyridine-2-carboxylic acid methyl ester

生成物 1

HCID 59596628
3-(2-Fluoro-4-trimethylsilanyl-phenylamino)-1-(2-triisopropylsilanyloxy-ethyl)-1H-pyrrolo[3,2-c]pyridine-2-carboxylic acid methyl ester
収率 88.4%

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A degassed solution of 3-amino-1-(2-triisopropylsilanyloxy-ethyl)-1H-pyrrolo[3,2-c]pyridine-2-carboxylic acid methyl ester (1.41 g, 3.61 mmol), trifluoro-methanesulfonic acid 2-fluoro-4-trimethylsilanyl-phenyl ester (1.48 g, 4.69 mmol), Pd2dba3 (165 mg, 0.18 mmol), Xantphos (208 mg, 0.36 mmol) and Cs2CO3 (2.35 g, 7.21 mmol) in toluene (30 ml) was heated to reflux then stirred for 16 hours. The reaction mixture was cooled to ambient temperature then diluted with EtOAc and filtered through a pad of celite. The resultant solution was concentrated in vacuo to give a black oil. The oil was purified by flash chromatography (Si-PPC, pentane:ether, gradient 100:0 to 0:100) to provide the title compound as a yellow oil (1.78 g, 88%). LCMS (method B): RT=3.76 min, M+H+=558.

後処理

  1. temperatureto reflux
  2. filtrationfiltered through a pad of celite
  3. concentrationThe resultant solution was concentrated in vacuo
  4. customto give a black oil
  5. customThe oil was purified by flash chromatography (Si-PPC, pentane:ether, gradient 100:0 to 0:100)

出典と根拠

ORDレコード
ord-b4017f2083ae4854a46baa80017785e9
出典データセット
uspto-grants-2010_12
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07855216B2

反応ノート

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