Sodium triacetoxyborohydride → HCID 86591722, compound

HRID 896550Notes

Reaction equation

HRID 896550 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH2:6][N:7]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:8][CH2:9][C:10]=1[NH:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:4].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(#N)C.C(O)(=O)C>[CH3:1][O:2][C:3]([C@H:5]1[C@@H:10]([NH:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:9][CH2:8][N:7]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:6]1)=[O:4]

Participants

5

Reactant 2

HCID 5049666Sodium triacetoxyborohydride2×HCID 69736395HCID 69736395, compound

Product 1

HCID 86591722HCID 86591722, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6342AcetonitrileSolvent

Procedure

A solution of crude 4-benzylamino-5,6-dihydro-2H-pyridine-1,3-dicarboxylic acid 1-tert-butyl ester 3-methyl ester (3.86 g, approximately 10 mmol) in acetonitrile (30 mL) and acetic acid (20 mL) was stirred on an ice bath and treated with sodium triacetoxyborohydride (4.83 g, 22.5 mmol). After 1.75 hours, additional sodium triacetoxyborohydride (4.82 g, 22.5 mmol) was added. After 2.25 hours, the mixture was concentrated under vacuum, and the residue was diluted with 1.0 N aqueous sodium hydroxide (50 mL), and the mixture was stirred on ice and the pH was adjusted to 10 with 50% aqueous sodium hydroxide. The mixture was extracted with dichloromethane, and the organic phase was dried over sodium sulfate and concentrated to provide an orange gum. Purification by flash chromatography with 40% ethyl acetate in hexane provided a colorless viscous oil (2.86 g, 82% for two steps). 1H NMR (300 MHz, CDCl3) δ7.4-7.3 (m, 5H), 4.03 (m, 1H), 3.88 (ab pattern, 2H), 3.73 (m, 1H), 3.71 (s, 3H), 3.38 (m, 1H), 3.20 (m, 1H), 3.12 (m, 1H), 2.90 (m, 1H), 1.91 (m, 1H), 1.78 (m, 1H), 1.46 (s, 9H).

Workup

  1. waitAfter 2.25 hours
  2. concentrationthe mixture was concentrated under vacuum
  3. additionthe residue was diluted with 1.0 N aqueous sodium hydroxide (50 mL)
  4. extractionThe mixture was extracted with dichloromethane
  5. dry with materialthe organic phase was dried over sodium sulfate
  6. concentrationconcentrated
  7. customto provide an orange gum
  8. customPurification by flash chromatography with 40% ethyl acetate in hexane
  9. customprovided a colorless viscous oil (2.86 g, 82% for two steps)

Sources & evidence

ORD record
ord-014e3201b4d242eb928322f43b615341
Source dataset
uspto-grants-2005_07
Patent number
US06919356B2

Reaction notes

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