1,2-Dichloroethane → methyl 2-bromo-7-(4-morpholinyl)-5H-pyrido[2',3':4,5]pyrrolo[2,3-b]pyridine-4-carboxylate

HRID 2410753

Reaction equation

ClCCCl.[N:5]([C:8]1[C:9]([C:19]2[CH:20]=[N:21][C:22]([N:25]3[CH2:30][CH2:29][O:28][CH2:27][CH2:26]3)=[CH:23][CH:24]=2)=[N:10][C:11]([Br:18])=[CH:12][C:13]=1[C:14]([O:16][CH3:17])=[O:15])=[N+]=[N-]>C1COCC1.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O.[Rh].[Rh]>[Br:18][C:11]1[CH:12]=[C:13]([C:14]([O:16][CH3:17])=[O:15])[C:8]2[NH:5][C:20]3=[N:21][C:22]([N:25]4[CH2:30][CH2:29][O:28][CH2:27][CH2:26]4)=[CH:23][CH:24]=[C:19]3[C:9]=2[N:10]=1

Participants

Conditions

Temperature: 80 °C

Procedure

1,2-Dichloroethane (0.4 mL) was added to a mixture of methyl 3-azido-6-bromo-6′-morpholino-2,3′-bipyridine-4-carboxylate (240 mg, 0.572 mmol), rhodium octanoate dimer (35.7 mg, 0.046 mmol) and crushed 4 A° molecular sieves (500 mg gm) and heated overnights at 80° C. The reaction was diluted with THF and filtered. The collected solid was washed with multiple portions of boiling THF to extract all of the product. The solvent was removed from the combined filtrates and the residue was suspended in MeOH and the product was collected by filtration. This left methyl 2-bromo-7-(4-morpholinyl)-5H-pyrido[2′,3′:4,5]pyrrolo[2,3-b]pyridine-4-carboxylate (167 mg, 0.427 mmol, 745% yield) as a yellow solid. 1H NMR (500 MHz, DMSO-d6) δ ppm 11.75 (1H, s), 8.30 (1H, d, J=8.85 Hz), 7.72 (1H, s), 6.91 (1H, d, J=8.85 Hz), 4.01 (3H, s), 3.74 (8H, dd, J=15.56, 4.88 Hz).

Workup

customcrushed 4 A° molecular sieves (500 mg gm)
filtrationfiltered
washThe collected solid was washed with multiple portions of boiling THF
extractionto extract all of the product
customThe solvent was removed from the combined filtrates
filtrationthe product was collected by filtration

Sources & evidence

ORD record: ord-ae1072e84508459d90a9512f50a1bc26
Source dataset: uspto-grants-2014_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08815840B2

Linked notes

Loading…