Sodium triacetoxyborohydride → HCID 69482270, compound

HRID 2364452Notes

Reaction equation

HRID 2364452 reaction equation
[NH2:1][C:2]1[C:3]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[N:4][CH:5]=[C:6]([CH2:8][C:9]2[CH:14]=[CH:13][C:12]([F:15])=[CH:11][CH:10]=2)[CH:7]=1.[CH3:21][N:22]([CH2:33][CH2:34][CH:35]=O)[C:23](=[O:32])[O:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(O)(=O)C>[F:15][C:12]1[CH:11]=[CH:10][C:9]([CH2:8][C:6]2[CH:7]=[C:2]([NH:1][CH2:35][CH2:34][CH2:33][N:22]([CH3:21])[C:23]([O:24][CH2:25][C:26]3[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=3)=[O:32])[C:3]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[N:4][CH:5]=2)=[CH:14][CH:13]=1

Participants

5

Reactant 3

HCID 5049666Sodium triacetoxyborohydride3×HCID 42637772Ethyl 3-amino-5-(4-fluorobenzyl)picolinateHCID 59854972HCID 59854972, compound2×

Product 1

HCID 69482270HCID 69482270, compound

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A mixture of ethyl 3-amino-5-(4-fluorobenzyl)-2-pyridinecarboxylate (1.21 g, 4.10 mmol) and phenylmethyl methyl(3-oxopropyl)carbamate (1.63 g, 7.39 mmol) in glacial acetic acid (15 mL) was treated with sodium trisacetoxyborohydride (1.74 g, 8.21 mmol) and stirred under nitrogen at ambient temperature. After approximately 1 hour, additional sodium triacetoxyborohydride (1.00 g, 4.72 mmol) was added. After an additional 3-4 hours, additional phenylmethyl methyl(3-oxopropyl)carbamate (1.00 g, 4.52 mmol) and sodium triacetoxyborohydride (1.00 g, 4.72 mmol) was added. The reaction mixture was evaporated in vacuo and the residue was dissolved in CH2Cl2 and treated with 2N KOH. After separating the layers, the aqueous phase was back-extracted with CH2Cl2 and the combined organic layers were washed with water, dried over MgSO4, filtered, evaporated in vacuo and purified on silica eluting with 3% MeOH in CH2Cl2 to provide the product as an oil: 1H NMR (CDCl3) δ 7.88 (1H, s), 7.77 (1H, s), 7.26-7.37 (5H, m), 7.11 (2H, b), 6.97 (2H, t, J=8.8), 6.74 (1H, d, J=31 Hz), 5.12 (2H, s), 4.42 (2H, q, J=7 Hz), 3.90 (2H, s), 3.41 (2H, t, J=7), 3.06-3.20 (2H, m), 2.92 (3H, s), 1.86 (2H, b), 1.42 (3H, t, J=7 Hz); ES+ MS: 480 (M+H+).

Workup

  1. waitAfter an additional 3-4 hours
  2. customThe reaction mixture was evaporated in vacuo
  3. dissolutionthe residue was dissolved in CH2Cl2
  4. additiontreated with 2N KOH
  5. customAfter separating the layers
  6. extractionthe aqueous phase was back-extracted with CH2Cl2
  7. washthe combined organic layers were washed with water
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customevaporated in vacuo
  11. custompurified on silica eluting with 3% MeOH in CH2Cl2

Sources & evidence

ORD record
ord-87345997578940608652823fcc030bee
Source dataset
uspto-grants-2014_04
Patent number
US08691991B2

Reaction notes

Loading…