1,2-Dichloroethane → methyl 2-bromo-7-(morpholinosulfonyl)-5H-pyrido[3,2-b]indole-4-carboxylate

HRID 2410867Notes

Reaction equation

ClCCCl.[N:5]([C:8]1[C:17]([C:18]2[CH:23]=[CH:22][C:21]([S:24]([N:27]3[CH2:32][CH2:31][O:30][CH2:29][CH2:28]3)(=[O:26])=[O:25])=[CH:20][CH:19]=2)=[N:16][C:15]([Br:33])=[CH:14][C:9]=1[C:10]([O:12][CH3:13])=[O:11])=[N+]=[N-]>C(Cl)Cl.CO.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O.[Rh].[Rh]>[Br:33][C:15]1[CH:14]=[C:9]([C:10]([O:12][CH3:13])=[O:11])[C:8]2[NH:5][C:19]3[CH:20]=[C:21]([S:24]([N:27]4[CH2:32][CH2:31][O:30][CH2:29][CH2:28]4)(=[O:26])=[O:25])[CH:22]=[CH:23][C:18]=3[C:17]=2[N:16]=1

Participants

Conditions

Temperature: 80 °C

Procedure

1,2-Dichloroethane (1.3 mL) was added to a mixture of methyl 3-azido-6-bromo-2-(4-(morpholinosulfonyl)phenyl)isonicotinate (918 mg, 1.90 mmol), rhodium octanoate dimer (74. mg, 0.095 mmol) and crushed 4A° molecular sieves (2.2 gm) and the reaction was heated at 80° C. overnight. It was then diluted with a mixture of DCM:MeOH (3:1) and filtered. The collected solid was washed with hot THF to extract any remaining product. The solvent was removed from the combined filtrates and the residue was suspended in MeOH. Filtration gave methyl 2-bromo-7-(morpholinosulfonyl)-5H-pyrido[3,2-b]indole-4-carboxylate (621 mg, 1.37 mmol, 72% yield) as a tan solid. 1H NMR (500 MHz, DMSO-d6) δ ppm 12.15 (1H, s), 8.47 (1H, d, J=8.24 Hz), 8.19 (1H, s), 8.04 (1H, s), 7.65 (1H, dd, J=8.24, 1.53 Hz), 3.63-3.72 (4H, m), 2.87-3.02 (5H, m).

Workup

customcrushed 4A° molecular sieves (2.2 gm)
filtrationfiltered
washThe collected solid was washed with hot THF
extractionto extract any remaining product
customThe solvent was removed from the combined filtrates
filtrationFiltration

Sources & evidence

ORD record: ord-e1d102f3d5fc46668993cb2bca2631ad
Source dataset: uspto-grants-2014_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08815840B2

Reaction notes

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