Sodium borohydride → 5-[1-(2-Chlorophenyl)-6-ethoxycarbonyl-6-methylheptyl]-4,5,6,7-tetrahydro-pyrrolo[3,2-c]pyridine-1-carboxylic acid tert-butyl ester

HRID 1526463Notes

Reaction equation

HRID 1526463 reaction equation
[Br-].[C:2]([O:6][C:7]([N:9]1[C:17]2[CH:16]=[CH:15][N+:14]([CH:18]([C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=3[Cl:32])[CH2:19][CH2:20][CH2:21][CH2:22][CH:23]([CH3:25])[CH3:24])=[CH:13][C:12]=2[CH:11]=[CH:10]1)=[O:8])([CH3:5])([CH3:4])[CH3:3].[BH4-].[Na+]>CCO>[C:2]([O:6][C:7]([N:9]1[C:17]2[CH2:16][CH2:15][N:14]([CH:18]([C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=3[Cl:32])[CH2:19][CH2:20][CH2:21][CH2:22][C:23]([C:7]([O:6][CH2:2][CH3:3])=[O:8])([CH3:24])[CH3:25])[CH2:13][C:12]=2[CH:11]=[CH:10]1)=[O:8])([CH3:4])([CH3:5])[CH3:3]

Participants

4

Reactant 2

HCID 4311764Sodium borohydride2×HCID 696696741-tert-butoxycarbonyl-5-[1-(2-chlorophenyl)-6-methylheptyl]-1H-pyrrolo[3,2-c]pyridin-5-ium bromide

Product 1

HCID 675180355-[1-(2-Chlorophenyl)-6-ethoxycarbonyl-6-methylheptyl]-4,5,6,7-tetrahydro-pyrrolo[3,2-c]pyridine-1-carboxylic acid tert-butyl esterYield 140.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 1-tert-butoxycarbonyl-5-[1-(2-chlorophenyl)-6-methylheptyl]-1H-pyrrolo[3,2-c]pyridin-5-ium bromide (2.4 g, 4.0 mmol) in 70% EtOH (60 mL) was added (at room temperature, with vigorous stirring, and in portions) sodium borohydride (0.30 g, 8.0 mmol). When the sodium borohydride was completely added, the stirring was terminated and mixture was stirred for 0.5 hours. The solvent was evaporated under reduced pressure and water (60 mL) was added. The product was extracted with dichloromethane (3×150 mL) and the combined organic extracts were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by column chromatography (silica gel, ethyl acetate/heptane=1/10 to 1/3) to yield 5-[1-(2-chlorophenyl)-6-ethoxycarbonyl-6-methylheptyl]-4,5,6,7-tetrahydro-pyrrolo[3,2-c]pyridine-1-carboxylic acid tert-butyl ester (1.45 g, 60.9% yield) as a yellow oil. 1H NMR (Field: 300 MHz, Solvent: CD3OD/TMS) δ (ppm): 7.50 (dd, 1H, J=7.5, 1.2 Hz), 7.37 (d, 1H, J=8.1, 1.5 Hz), 7.27-7.10 (m, 3H), 5.94 (d, 1H, J=3.3 Hz), 4.16-4.13 (m, 1H), 4.09 (q, 2H, J=6.9 Hz), 3.62 (d, 1H, J=14.1 Hz), 3.28 (d, 1H, J=13.5 Hz), 2.85-2.60 (m, 4H), 1.98-1.76 (m, 2H), 1.55 (s, 9H), 1.42 (t, 2H, J=6.9 Hz), 1.28-1.16 (m, 4H), 1.21 (t, 3H, J=7.2 Hz), 1.11 (s, 6H). 13C NMR (Field: 75 MHz, Solvent: CDCl3/TMS) δ (ppm): 177.98, 149.49, 139.66, 134.90, 129.44, 129.15, 127.93, 127.60, 126.84, 120.92, 119.77, 109.20, 83.26, 63.76, 60.33, 48.81, 48.19, 42.30, 40.80, 33.23, 32.13, 28.31, 26.07, 25.35, 22.96, 14.52. HRMS (DART-TOF): Calculated for C20H41ClN2O2 (M+H)+: 517.2828. found 517.2833.

Workup

  1. customthe stirring was terminated
  2. customThe solvent was evaporated under reduced pressure and water (60 mL)
  3. additionwas added
  4. extractionThe product was extracted with dichloromethane (3×150 mL)
  5. dry with materialthe combined organic extracts were dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe crude residue was purified by column chromatography (silica gel, ethyl acetate/heptane=1/10 to 1/3)

Sources & evidence

ORD record
ord-9ac9c4003fe042ebb0030940beb20e97
Source dataset
uspto-grants-2015_07
Patent number
US09085585B2

Reaction notes

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