Sodium Dithionite → tert-butyl 4-(7-(4-benzylpiperidin-1-yl)-6-bromo-3H-imidazo[4,5-b]pyridin-2-yl)benzylcarbamate

HRID 416868Notes

Reaction equation

HRID 416868 reaction equation
BrC1C(N2CCN(C(NC3C=CC=CC=3)=O)CC2)=C2N=C(C3C=CC(N(C)C)=CC=3)NC2=NC=1.[CH2:35]([CH:42]1[CH2:47][CH2:46][N:45]([C:48]2[C:53]([Br:54])=[CH:52][N:51]=[C:50]([NH2:55])[C:49]=2[N+:56]([O-])=O)[CH2:44][CH2:43]1)[C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1.[O-]S(S([O-])=O)=O.[Na+].[Na+].[CH:67]([C:69]1[CH:83]=[CH:82][C:72]([CH2:73][NH:74][C:75](=[O:81])[O:76][C:77]([CH3:80])([CH3:79])[CH3:78])=[CH:71][CH:70]=1)=O>C(O)C.CN(C=O)C>[CH2:35]([CH:42]1[CH2:47][CH2:46][N:45]([C:48]2[C:53]([Br:54])=[CH:52][N:51]=[C:50]3[NH:55][C:67]([C:69]4[CH:83]=[CH:82][C:72]([CH2:73][NH:74][C:75](=[O:81])[O:76][C:77]([CH3:80])([CH3:78])[CH3:79])=[CH:71][CH:70]=4)=[N:56][C:49]=23)[CH2:44][CH2:43]1)[C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1

Participants

7

Reactant 4

HCID 24489Sodium DithioniteHCID 2794832tert-Butyl hydrogen ((4-formylphenyl)methyl)carbonimidateHCID 578971604-(4-Benzylpiperidin-1-yl)-5-bromo-3-nitropyridin-2-amineHCID 178482685HCID 178482685, compound

Product 1

HCID 178453032tert-butyl 4-(7-(4-benzylpiperidin-1-yl)-6-bromo-3H-imidazo[4,5-b]pyridin-2-yl)benzylcarbamateYield 22.2%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6228DimethylformamideSolvent

Procedure

This was prepared using the same procedure as for 4-(6-bromo-2-(4-(dimethylamino)phenyl)-3H-imidazo[4,5-b]pyridin-7-yl)-N-phenylpiperazine-1-carboxamide, but here using 4-(4-benzylpiperidin-1-yl)-5-bromo-3-nitropyridin-2-amine (100 mg, 0.25 mmol), DMF (0.20 mL), ethanol (1.25 mL), 1M Na2S2O4 (3 eq, 0.75 mmol, 0.75 mL) and tert-butyl N-(4-formylbenzyl)carbamate (1.1 eq, 0.28 mmol, 66 mg). After 6 h, concentration in vacuo and purification by preparative tlc (CH2Cl2-MeOH, 95:5) gave the product (32 mg, 22%) as a colourless solid; δH (500 MHz, DMSO-d6) 1.41 (s, 9H, C(CH3)3), 1.44-1.49 (m, 2H, 2× piperidine CHAHB), 1.73 (app d, J=11.0 Hz, 2H, 2× piperidine CHAHB), 1.78-1.85 (m, 1H, piperidine CH), 2.61 (app d, J=7.1 Hz, 2H, PhCH2), 3.31-3.34 (m, 2H, 2× piperidine NCHAHA), 3.85 (app d, J=11.9 Hz, 2H, 2× piperidine NCHAHA), 4.19 (d, J=7.9 Hz, 2H, CH2—NHBOC), 7.20 (t, J=7.3 Hz, 1H, phenyl H-4), 7.23 (d, J=7.0 Hz, 2H, phenyl H-2 & H-6), 7.31 (t, br, J=7.4 Hz, 2H, phenyl H-3 & H-5), 7.38 (d, J=8.2 Hz, 2H, phenyl H-3′ & H-5′), 7.43 (t, br, J=5.9 Hz, 1H, CH2—NHBOC), 8.11 (d, J=8.9 Hz, 2H, phenyl H-2′ & H-6′), 8.21 (s, 1H, imidazo[4,5-b]pyridine H-5), 13.03 (s, br, 1H, imidazo[4,5-b]pyridine NH);

Workup

  1. customThis was prepared
  2. concentrationconcentration
  3. customin vacuo and purification by preparative tlc (CH2Cl2-MeOH, 95:5)

Sources & evidence

ORD record
ord-8bca147d24e14bf397175cca3c39f2a1
Source dataset
uspto-grants-2012_01
Patent number
US08088761B2

Reaction notes

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