(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

Reaktionsgleichung

Reaktionsgleichung von HRID 1484945
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]

Komponenten

5

Edukt 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

Produkt 1

HCID 58169526(Z)-N-tert-butyl-5-(4-(5-cyclopropyl-1H-pyrazol-3-ylamino)-5-(prop-1-enyl)pyrimidin-2-yl)thiophene-2-sulfonamideAusbeute 82,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 74236Tetrabutylammonium BromideKatalysatorHCID 178418476HCID 178418476, VerbindungKatalysator

Versuchsvorschrift

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]+.

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-4ca8fced5c7e4b0d8bfd489192d71c72
Quelldatensatz
uspto-grants-2016_08
Patentnummer
US09422271B2

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