Stannanecarbonitrile, tributyl- → Tert-butyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-6-cyano-3-(6-phenylpyridin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)piperidine-1-carboxylate

HRID 2047146Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2047146
[CH3:1][Si:2]([CH3:52])([CH3:51])[CH2:3][CH2:4][O:5][CH2:6][N:7]([CH2:43][O:44][CH2:45][CH2:46][Si:47]([CH3:50])([CH3:49])[CH3:48])[C:8]1[N:13]2[N:14]=[CH:15][C:16]([C:17]3[CH:18]=[N:19][C:20]([C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)=[CH:21][CH:22]=3)=[C:12]2[N:11]=[C:10]([CH:29]2[CH2:34][CH2:33][N:32]([C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[CH2:31][CH2:30]2)[C:9]=1Br.[Sn]([C:66]#[N:67])(CCCC)(CCCC)CCCC>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.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH3:1][Si:2]([CH3:52])([CH3:51])[CH2:3][CH2:4][O:5][CH2:6][N:7]([CH2:43][O:44][CH2:45][CH2:46][Si:47]([CH3:50])([CH3:49])[CH3:48])[C:8]1[N:13]2[N:14]=[CH:15][C:16]([C:17]3[CH:18]=[N:19][C:20]([C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)=[CH:21][CH:22]=3)=[C:12]2[N:11]=[C:10]([CH:29]2[CH2:34][CH2:33][N:32]([C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[CH2:31][CH2:30]2)[C:9]=1[C:66]#[N:67]

Komponenten

5

Edukt 2

HCID 200512Stannanecarbonitrile, tributyl-HCID 66584941Tert-butyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-6-bromo-3-(6-phenylpyridin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)piperidine-1-carboxylate

Produkt 1

HCID 66737967Tert-butyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-6-cyano-3-(6-phenylpyridin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)piperidine-1-carboxylateAusbeute 84 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 178418851HCID 178418851, VerbindungKatalysator

Versuchsvorschrift

To a Schenk tube were charged compound tert-butyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-6-bromo-3-(6-phenylpyridin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)piperidine-1-carboxylate (81 mg, 0.1 mmol), Bu3SnCN (47 mg, 1.5 eq.), Pd(PPh3)4 (23 mg, 0.2 eq.), Bis(tri-t-butylphosphine)palladium (0) (10 mg, O2 eq.). The tube was evacuated and charged with Ar for three cycles. Dioxane (3 ml) was added; the tube was capped and heated at 160 C with stirring for one hour. After cooling, the mixture was diluted with EtOAc and washed with brine once. Organic layer separated, dried over MgSO4 and concentrated. The residue was purified on silica gel. Elution with EtOAc/hexane (0-25%) gave the desired title product (63 mg, 84%).

Aufarbeitung

  1. customThe tube was evacuated
  2. additioncharged with Ar for three cycles
  3. additionDioxane (3 ml) was added
  4. customthe tube was capped
  5. temperatureheated at 160 C
  6. temperatureAfter cooling
  7. additionthe mixture was diluted with EtOAc
  8. washwashed with brine once
  9. customOrganic layer separated
  10. dry with materialdried over MgSO4
  11. concentrationconcentrated
  12. customThe residue was purified on silica gel
  13. washElution with EtOAc/hexane (0-25%)

Quellen und Nachweise

ORD-Eintrag
ord-1b3e3960a03e44d2956ccab7d6113f5d
Quelldatensatz
uspto-grants-2013_11
Patentnummer
US08591943B2

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