tert-Butyl 4-(2-oxo-2,3-dihydro-1H-benzo[d]imidazol-5-yl)-5,6-dihydropyridine-1(2H)-carboxylate → tert-Butyl 4-(2-oxo-2,3-dihydro-1H-benzo[d]imidazol-5-yl)piperidine-1-carboxylate

HRID 1397893Notes

Reaction equation

HRID 1397893 reaction equation
[O:1]=[C:2]1[NH:6][C:5]2[CH:7]=[CH:8][C:9]([C:11]3[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH:12]=3)=[CH:10][C:4]=2[NH:3]1>CO.[Ni]>[O:1]=[C:2]1[NH:6][C:5]2[CH:7]=[CH:8][C:9]([CH:11]3[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]3)=[CH:10][C:4]=2[NH:3]1

Participants

4

Reactant 1

HCID 117722369tert-Butyl 4-(2-oxo-2,3-dihydro-1H-benzo[d]imidazol-5-yl)-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 117716866tert-Butyl 4-(2-oxo-2,3-dihydro-1H-benzo[d]imidazol-5-yl)piperidine-1-carboxylateYield 90%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

For synthesis from compound 16, following the same procedure adopted for the synthesis of 13, the title compound 17 was obtained from the reaction of compound 16 with CDI. Yield: 62%, off-white solid. For synthesis from compound 13, to a solution of compound 13 (0.94 g, 3 mmol) in CH3OH (30 mL) was added Ra—Ni (0.20 g, 10% wet basis), and the mixture was subjected to hydrogenation in a Parr apparatus at 60 psi for 12 hours. After filtering over the pad of celite, the solution was concentrated and recrystallized from diethyl ether to get compound 17. Yield: 90%, off-white solid, mp>250° C. IR (KBr, cm1) 3290, 3175 (CONH), 3030 (Ar—H), 2989 (Alph-H), 1691 (CO), 1613, 1515, 1416 (C═C), 1220 (C—N), 1167 (C-0); 1H NMR (500 MHz, DMSO d6) δ 1.38 (s, 9H, OC(CH3)3), 1.86 (m, al, CH2), 2.06 (m, 211, CH2), 2.40-2.48 (m, 3H, CH, CH2), 3.44 (obscured by H2O, 2H, CH2), 6.70-6.80 (m, 3H, H-4, H-6, H-7), 10.49 (br. s, 1H, NH), 10.53 (br. s, 1H, NH). 13C NMR (125.7 MHz, DMSO d6) δ 28.15 (OC(CH3)3), 29.25 (CH2), 33.24 (CH2), 41.72 (CH2), 78.72 (OC(CH3)3), 106.93 (C-4), 108.48 (C-7), 119.0 (C-6), 128.09 (C-8), 129.89 (C-9), 138.49 (C-5), 154.05 (CO), 155.61 (CO). Anal. Calcd for C17H23N3O3: C, 64.33; H, 7.30; N, 13.24%. Found: C, 64.25; H, 7.35; N, 13.15%.

Workup

  1. filtrationAfter filtering over the pad of celite
  2. concentrationthe solution was concentrated
  3. customrecrystallized from diethyl ether

Sources & evidence

ORD record
ord-d4b111affd574e1ba3a8c72f7e9741b8
Source dataset
uspto-grants-2014_12
Patent number
US08901304B1

Reaction notes

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