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 521765Notes

Reaction equation

HRID 521765 reaction equation
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]

Participants

5

Reactant 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

Product 1

HCID 67042276methyl 5-(4-(tert-butoxycarbonyl(3-nitrophenyl)amino)pyridine-2-yl)-1H-pyrrole-3-carboxylateYield 543.8%

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
105 °C

Procedure

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 Pd2dba3 (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.

Workup

  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

Sources & evidence

ORD record
ord-4ec5e8df3ab54471b60320df69684ed0
Source dataset
uspto-grants-2016_05
Patent number
US09328103B2

Reaction notes

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