Dichloromethane → Methyl (65)-2'-oxo-1'-{[2-(trimethylsilyl)ethoxy]methyl}-1',2',5,7-tetrahydrospiro[cyclopenta[b]pyridine-6,3'-pyrrolo[2,3-b]pyridine]-3-carboxylate

HRID 1404474Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1404474
Br[C:2]1[CH:3]=[C:4]2[CH2:27][C:9]3([C:17]4[C:12](=[N:13][CH:14]=[CH:15][CH:16]=4)[N:11]([CH2:18][O:19][CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[C:10]3=[O:26])[CH2:8][C:5]2=[N:6][CH:7]=1.[CH2:28](Cl)Cl.[C:31]([O-:34])(=[O:33])C.[Na+].[C]=O>CO.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[O:26]=[C:10]1[N:11]([CH2:18][O:19][CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[C:12]2=[N:13][CH:14]=[CH:15][CH:16]=[C:17]2[C@@:9]21[CH2:8][C:5]1=[N:6][CH:7]=[C:2]([C:31]([O:34][CH3:28])=[O:33])[CH:3]=[C:4]1[CH2:27]2

Komponenten

7

Edukt 4

HCID 6344DichloromethaneHCID 517045Sodium AcetateHCID 68749705HCID 68749705, VerbindungHCID 178418416HCID 178418416, Verbindung

Produkt 1

HCID 86665189Methyl (65)-2'-oxo-1'-{[2-(trimethylsilyl)ethoxy]methyl}-1',2',5,7-tetrahydrospiro[cyclopenta[b]pyridine-6,3'-pyrrolo[2,3-b]pyridine]-3-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 887MethanolLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

A mixture of 3-bromo-1′-{[2-(trimethylsilyl)ethoxy]methyl}-5,7-dihydrospiro[cyclopenta[b]pyridine-6,3′-pyrrolo[2,3-b]pyridin]-2′(1′H)-one (22.0 g, 49.3 mmol), PdCl2(dppf).CH2Cl2 (2.012 g, 2.46 mmol), and sodium acetate (8.1 g, 99 mmol) in in methanol (150 mL) was pressurized to 300 psi of carbon monoxide and then heated at 85° C. for 72 h. The reaction mixture was allowed to cool then concentrated. The residue was purified via silica gel chromatography (heptane initially, grading to 100% EtOAc) to give the title compound as a racemic mixture. MS: m/z=426.1 (M+1). Resolution of the enantiomers by supercritical fluid chromatography (SFC) using a ChiralPak® AD-H column and eluting with 40% ethanol in CO2 (0.05% diethylamine as modifier) provided the title compound as the second enantiomer to elute.

Aufarbeitung

  1. temperatureto cool
  2. concentrationthen concentrated
  3. customThe residue was purified via silica gel chromatography (heptane initially

Quellen und Nachweise

ORD-Eintrag
ord-97a1e21514d940c4ba39cbd1f4f1affc
Quelldatensatz
uspto-grants-2014_12
Patentnummer
US08912210B2

Notizen zur Reaktion

Wird geladen…