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2-Isopropoxy-6-(tributylstannyl)pyridine → tert-butyl (3-(3-(6-isopropoxypyridin-2-yl)-1-tosyl-1H-indol-5-yl)-1,2,4-thiadiazol-5-yl)carbamate

HRID 634263
ノート
印刷プレビュー

反応式

HRID 634263 の反応式
I[C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[C:8]([C:11]3[N:15]=[C:14]([NH:16][C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])[S:13][N:12]=3)[CH:9]=2)[N:4]([S:24]([C:27]2[CH:33]=[CH:32][C:30]([CH3:31])=[CH:29][CH:28]=2)(=[O:26])=[O:25])[CH:3]=1.[CH:34]([O:37][C:38]1[CH:43]=[CH:42][CH:41]=[C:40]([Sn](CCCC)(CCCC)CCCC)[N:39]=1)([CH3:36])[CH3:35]>CN(C=O)C.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:34]([O:37][C:38]1[N:39]=[C:40]([C:2]2[C:10]3[C:5](=[CH:6][CH:7]=[C:8]([C:11]4[N:15]=[C:14]([NH:16][C:17](=[O:23])[O:18][C:19]([CH3:21])([CH3:20])[CH3:22])[S:13][N:12]=4)[CH:9]=3)[N:4]([S:24]([C:27]3[CH:33]=[CH:32][C:30]([CH3:31])=[CH:29][CH:28]=3)(=[O:25])=[O:26])[CH:3]=2)[CH:41]=[CH:42][CH:43]=1)([CH3:36])[CH3:35]
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

6

反応物 2

HCID 683286192-Isopropoxy-6-(tributylstannyl)pyridineHCID 86725113tert-butyl 3-(3-iodo-1-tosyl-1H-indol-5-yl)-1,2,4-thiadiazol-5-ylcarbamate

生成物 1

HCID 86725114tert-butyl (3-(3-(6-isopropoxypyridin-2-yl)-1-tosyl-1H-indol-5-yl)-1,2,4-thiadiazol-5-yl)carbamate収率 57.8%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒
HCID 178418397HCID 178418397、化合物触媒
HCID 6228Dimethylformamide溶媒

反応条件

温度
90 °C

実験手順

A mixture of tert-butyl (3-(3-iodo-1-tosyl-1H-indol-5-yl)-1,2,4-thiadiazol-5-yl)carbamate (0.6 g, 1.0 mmol) and 2-isopropoxy-6-(tributylstannyl)pyridine (0.429 g, 1.0 mmol) in DMF (10 mL) was bubbled N2 gas for 15 min. To the above mixture, CuI (95 mg, 0.5 mmol.) and Pd(PPh3)4 (12 mg, 0.1 mmol) were added and N2 gas was bubbled for another 15 min. The reaction was heated at 90° C. for 1 h. The reaction mixture was quenched with H2O (10 mL) and extracted with CHCl3 (2×25 mL). The organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude was purified by neutral alumina column chromatography (eluent: 20% EtOAc in petroleum ether) to give tert-butyl (3-(3-(6-isopropoxypyridin-2-yl)-1-tosyl-1H-indol-5-yl)-1,2,4-thiadiazol-5-yl)carbamate (0.35 g, 57.4%). MS (ESI, pos. ion) m/z: 606.4 (M+1); 1H NMR (DMSO-d6, 400 MHz): δ 9.33 (s, 1H), 8.52 (s, 1H), 8.16-8.08 (m, 2H), 7.97 (d, J=8 Hz, 2H), 7.76 (t, J=7.6 Hz, 1H), 7.63 (d, J=7.6 Hz, 2H), 7.40 (d, J=8.4 Hz, 1H), 6.69 (d, J=8 Hz, 1H), 5.52-5.49 (m, 1H), 2.30 (s, 3H), 1.40 (d, J=6 Hz, 6H).

後処理

  1. customwas bubbled N2 gas for 15 min
  2. customN2 gas was bubbled for another 15 min
  3. customThe reaction mixture was quenched with H2O (10 mL)
  4. extractionextracted with CHCl3 (2×25 mL)
  5. dry with materialThe organic layer was dried over anhydrous Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. customThe crude was purified by neutral alumina column chromatography (eluent: 20% EtOAc in petroleum ether)

出典と根拠

ORDレコード
ord-cb175bdc7ea941ba9d2006a7b65178e6
出典データセット
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09321756B2

反応ノート

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