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

HRID 2410758Notes

Reaction equation

HRID 2410758 reaction equation
ClCCCl.[N:5]([C:8]1[C:17]([C:18]2[CH:23]=[CH:22][C:21]([O:24][CH2:25][C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=3)=[CH:20][CH:19]=2)=[N:16][C:15]([Br:32])=[CH:14][C:9]=1[C:10]([O:12][CH3:13])=[O:11])=[N+]=[N-]>C(Cl)Cl.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O.[Rh].[Rh]>[CH2:25]([O:24][C:21]1[CH:20]=[CH:19][C:18]2[C:17]3[N:16]=[C:15]([Br:32])[CH:14]=[C:9]([C:10]([O:12][CH3:13])=[O:11])[C:8]=3[NH:5][C:23]=2[CH:22]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

5

Reactant 2

HCID 111,2-DichloroethaneHCID 86663025Methyl 3-azido-2-(4-(benzyloxy)phenyl)-6-bromoisonicotinate

Product 1

HCID 86663026methyl 7-(benzyloxy)-2-bromo-5H-pyrido[3,2-b]indole-4-carboxylateYield 81%

Reagents, catalysts & solvents 2

HCID 6099591Rhodium(II) Octanoate DimerCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
60 °C

Procedure

1,2-Dichloroethane (3.5 mL) was added to a mixture of methyl 3-azido-2-(4-(benzyloxy)phenyl)-6-bromoisonicotinate (2.28 g, 5.19 mmol), rhodium octanoate dimer (0.101 g, 0.130 mmol) and crushed 4 A° molecular sieves (2.2 gm). This was heated at 60° C. for 6 hr. The reaction was diluted with a mixture of DCM:MeOH=3:1 and filtered. The collected solid was washed with additional DCM:MeOH mixture to dissolve any remaining product. The solvent was removed from the filtrate and the residue was suspended in MeOH. The product was collected by filtration and washed with a little MeOH to leave methyl 7-(benzyloxy)-2-bromo-5H-pyrido[3,2-b]indole-4-carboxylate (1.72 g, 4.18 mmol, 81% yield) as a yellow solid. MS (ESI) m/z 412.9 (M+H). 1H NMR (400 MHz, chloroform-d) δ ppm 9.45 (1H, br. s.), 8.22 (1H, d, J=8.81 Hz), 7.87 (1H, s), 7.43-7.50 (2H, m), 7.37-7.44 (2H, m), 7.30-7.37 (1H, m), 6.96-7.06 (2H, m), 5.18 (2H, s), 4.04 (3H, s).

Workup

  1. customcrushed 4 A° molecular sieves (2.2 gm)
  2. filtrationMeOH=3:1 and filtered
  3. washThe collected solid was washed with additional DCM
  4. dissolutionMeOH mixture to dissolve any remaining product
  5. customThe solvent was removed from the filtrate
  6. filtrationThe product was collected by filtration
  7. washwashed with a little MeOH

Sources & evidence

ORD record
ord-6a3c144ace92454492455989d555fbcc
Source dataset
uspto-grants-2014_08
Patent number
US08815840B2

Reaction notes

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