Tributylstannane → 3-[4-(8-Aza-bicyclo[3.2.1]oct-8-ylmethyl)-phenyl]-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile

HRID 1505945Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1505945
[C:1]([C:3]1[N:11]=[CH:10][C:9]2[N:8]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[C:7]3[N:20]=[CH:21][C:22]([C:24]4[CH:46]=[CH:45][C:27]([CH2:28][N:29]5[CH:34]6[CH2:35][CH2:36][CH:30]5[CH2:31][CH:32](OC(N5C=CN=C5)=S)[CH2:33]6)=[CH:26][CH:25]=4)=[CH:23][C:6]=3[C:5]=2[CH:4]=1)#[N:2].CC(N=NC(C#N)(C)C)(C#N)C.C([SnH](CCCC)CCCC)CCC>C1(C)C=CC=CC=1>[CH:34]12[N:29]([CH2:28][C:27]3[CH:45]=[CH:46][C:24]([C:22]4[CH:21]=[N:20][C:7]5[N:8]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:17])([CH3:18])[CH3:19])[C:9]6[CH:10]=[N:11][C:3]([C:1]#[N:2])=[CH:4][C:5]=6[C:6]=5[CH:23]=4)=[CH:25][CH:26]=3)[CH:30]([CH2:36][CH2:35]1)[CH2:31][CH2:32][CH2:33]2

Komponenten

5

Edukt 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 58266558Imidazole-1-carbothioic acid O-(8-{4-[6-cyano-9-(2-trimethylsilanylethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrol-3-yl]-benzyl}-8-aza-bicyclo[3.2.1]oct-3-yl)ester

Produkt 1

HCID 582665503-[4-(8-Aza-bicyclo[3.2.1]oct-8-ylmethyl)-phenyl]-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrileAusbeute 84 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

To a solution of imidazole-1-carbothioic acid O-(8-{4-[6-cyano-9-(2-trimethylsilanylethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrol-3-yl]-benzyl}-8-aza-bicyclo[3.2.1]oct-3-yl) ester (182 mg, 0.28 mmol) and AIBN (60 mg, 0.36 mmol) in toluene (10 mL) under an argon atmosphere was added tributyltin hydride (0.58 mL, 1.85 mmol). On complete addition, the reaction was heated at 110° C. for 15 minutes then allowed to cool to ambient temperature. The mixture was concentrated in vacuo and the resultant residue was purified by flash chromatography (silica, 50 g column, Biotage, 0-5% MeOH in DCM) to afford the title compound as a white solid (123 mg, 84%). 1H NMR (CDCl3, 300 MHz): 9.26 (d, J=1.0 Hz, 1H), 9.03 (d, J=2.2 Hz, 1H), 8.69 (d, J=2.2 Hz, 1H), 8.51 (d, J=1.0 Hz, 1H), 7.72-7.60 (m, 4H), 6.12 (s, 2H), 3.74-3.65 (m, 4H), 3.37-3.22 (m, 2H), 2.16-1.40 (m, 10H), 1.06-0.97 (m, 2H), 0.00 (s, 9H). LCMS (Method B): RT=2.96 min, M+H+=524.

Aufarbeitung

  1. additionOn complete addition
  2. temperatureto cool to ambient temperature
  3. concentrationThe mixture was concentrated in vacuo
  4. customthe resultant residue was purified by flash chromatography (silica, 50 g column, Biotage, 0-5% MeOH in DCM)

Quellen und Nachweise

ORD-Eintrag
ord-48f8b335f83742fd90060526a851f085
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09216980B2

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