1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) → methyl 5-(4-(tert-butoxycarbonyl(3-nitrophenyl)amino)pyridine-2-yl)-1H-pyrrole-3-carboxylate

HRID 1915046Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1915046
Cl[C:2]1[CH:7]=[C:6]([N:8]([C:16]2[CH:21]=[CH:20][CH:19]=[C:18]([N+:22]([O-:24])=[O:23])[CH:17]=2)[C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=[CH:4][N:3]=1.CC1(C)C(C)(C)OB([C:33]2[NH:37][CH:36]=[C:35]([C:38]([O-:40])=[O:39])[CH:34]=2)O1.[CH3:42]C1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:11]([O:10][C:9]([N:8]([C:16]1[CH:21]=[CH:20][CH:19]=[C:18]([N+:22]([O-:24])=[O:23])[CH:17]=1)[C:6]1[CH:5]=[CH:4][N:3]=[C:2]([C:33]2[NH:37][CH:36]=[C:35]([C:38]([O:40][CH3:42])=[O:39])[CH:34]=2)[CH:7]=1)=[O:15])([CH3:14])([CH3:13])[CH3:12]

Komponenten

5

Edukt 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 58167904tert-Butyl 2-chloropyridin-4-yl(3-nitrophenyl)carbamateHCID 866515565-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole-3-carboxylate

Produkt 1

HCID 67042276methyl 5-(4-(tert-butoxycarbonyl(3-nitrophenyl)amino)pyridine-2-yl)-1H-pyrrole-3-carboxylateAusbeute 543,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysator

Reaktionsbedingungen

Temperatur
105 °C

Versuchsvorschrift

A mixture of tert-Butyl 2-chloropyridin-4-yl(3-nitrophenyl)carbamate (3.65 g, 10.43 mmol), methyl-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole-3-carboxylate (5.48 g, 21.82 mmol), xantphos (0.72 g, 1.25 mmol) and Pd2 dba3 (0.72 g, 0.79 mmol) was added to a thick walled reaction vessel and purged with N2. A solution of 2M K2CO3 (8.76 mL) was added, followed by dioxane (67 mL). The reaction vessel was sealed and the mixture stirred at 105° C. for 18 h. The reaction vessel was cooled to rt and the mixture was filtered over celite, washing with EtOAc. The filtrate was concentrated to afford a dark oil, which was purified via column chromatography eluting with 30-50% EtOAc/hexanes to afford methyl 5-(4-(tert-butoxycarbonyl(3-nitrophenyl)amino)pyridine-2-yl)-1H-pyrrole-3-carboxylate (2.98 g, 65% yield) as an orange oil.

Aufarbeitung

  1. additionwas added to a thick walled reaction vessel
  2. custompurged with N2
  3. additionA solution of 2M K2CO3 (8.76 mL) was added
  4. customThe reaction vessel was sealed
  5. temperatureThe reaction vessel was cooled to rt
  6. filtrationthe mixture was filtered over celite
  7. washwashing with EtOAc
  8. concentrationThe filtrate was concentrated
  9. customto afford a dark oil, which
  10. customwas purified via column chromatography
  11. washeluting with 30-50% EtOAc/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-4d717403e4bb427ba1ec2e2ef93036ea
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08614234B2

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