(Z)-Tri-n-butyl(1-propenyl)tin → (Z)-N-tert-butyl-5-(4-(5-cyclopropyl-1H-pyrazol-3-ylamino)-5-(prop-1-enyl)pyrimidin-2-yl)thiophene-2-sulfonamide

HRID 1484945

反応式

HRID 1484945 の反応式
Br[C:2]1[C:3]([NH:21][C:22]2[CH:26]=[C:25]([CH:27]3[CH2:29][CH2:28]3)[NH:24][N:23]=2)=[N:4][C:5]([C:8]2[S:12][C:11]([S:13]([NH:16][C:17]([CH3:20])([CH3:19])[CH3:18])(=[O:15])=[O:14])=[CH:10][CH:9]=2)=[N:6][CH:7]=1.[CH2:30]([Sn](CCCC)(CCCC)/C=C\C)[CH2:31][CH2:32]C>[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-].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>[C:17]([NH:16][S:13]([C:11]1[S:12][C:8]([C:5]2[N:4]=[C:3]([NH:21][C:22]3[CH:26]=[C:25]([CH:27]4[CH2:29][CH2:28]4)[NH:24][N:23]=3)[C:2](/[CH:30]=[CH:31]\[CH3:32])=[CH:7][N:6]=2)=[CH:9][CH:10]=1)(=[O:15])=[O:14])([CH3:20])([CH3:19])[CH3:18]

参加物

5

反応物 2

HCID 10914524(Z)-Tri-n-butyl(1-propenyl)tinHCID 581693555-(5-bromo-4-(5-cyclopropyl-1H-pyrazol-3-ylamino)pyrimidin-2-yl)-N-tert-butylthiophene-2-sulfonamide

生成物 1

HCID 58169526(Z)-N-tert-butyl-5-(4-(5-cyclopropyl-1H-pyrazol-3-ylamino)-5-(prop-1-enyl)pyrimidin-2-yl)thiophene-2-sulfonamide収率 82.1%

試薬・触媒・溶媒 2

HCID 74236Tetrabutylammonium Bromide触媒HCID 178418476HCID 178418476、化合物触媒

実験手順

A mixture of 5-(5-bromo-4-(5-cyclopropyl-1H-pyrazol-3-ylamino)pyrimidin-2-yl)-N-tert-butylthiophene-2-sulfonamide (497.4 mg, 1.0 mmol, 1.0 eq), Pd(PPh3)2Cl2 (28.0 mg, 0.1 mmol, 0.1 eq) and Bu4NBr (321.1 mg, 0.1 mmol, 1.0 equiv.) was flushed with nitrogen. Anhydrous dioxane (10 mL) was added and the reaction mixture was flushed with nitrogen. (Z)-tributyl(prop-1-enyl)stannane (475.4 mg, 1.5 mmol, 1.5 eq) was added and the reaction mixture was stirred at rt for 2 h. The mixture was extracted with EtOAc and washed with water, brine. The organic layers were concentrated to afford the residue, which was purified by silica gel chromatography (PE/EA/MeOH=2:1:0.06 as eluant) to afford (Z)—N-tert-butyl-5-(4-(5-cyclopropyl-1H-pyrazol-3-ylamino)-5-(prop-1-enyl)pyrimidin-2-yl)thiophene-2-sulfonamide (375.6 mg, 82.1%) as white solid. LC-MS (m/z)=459 [M+H]+.

後処理

  1. customwas flushed with nitrogen
  2. additionAnhydrous dioxane (10 mL) was added
  3. customthe reaction mixture was flushed with nitrogen
  4. extractionThe mixture was extracted with EtOAc
  5. washwashed with water, brine
  6. concentrationThe organic layers were concentrated
  7. customto afford the residue, which
  8. customwas purified by silica gel chromatography (PE/EA/MeOH=2:1:0.06 as eluant)

出典と根拠

ORDレコード
ord-4ca8fced5c7e4b0d8bfd489192d71c72
出典データセット
uspto-grants-2016_08
特許番号
US09422271B2

関連ノート

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