Sodium triacetoxyborohydride → HCID 69482217, compound

HRID 2364538Notes

Reaction equation

HRID 2364538 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.[O:21]=[C:22]1[CH2:27][CH2:26][CH2:25][CH2:24][N:23]1[CH2:28][CH2:29][CH:30]=O.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][CH2:30][CH2:29][CH2:28][N:23]3[CH2:24][CH2:25][CH2:26][CH2:27][C:22]3=[O:21])[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 63040760HCID 63040760, compound3×

Product 1

HCID 69482217HCID 69482217, compound

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A solution of ethyl 3-amino-5-(4-fluorobenzyl)-2-pyridinecarboxylate (0.79 g, 2.9 mmol) and 3-(2-oxo-1-piperidinyl)propanal (0.56 g, 3.6 mmol) under nitrogen in glacial acetic acid (10 mL) was treated with sodium triacetoxyborohydride (1.21 g, 5.7 mmol) at 0° C. for 30 min. After stirring for an additional 30 min., an additional 0.23 g of 3-(2-oxo-1-piperidinyl)propanal and 0.36 g sodium triacetoxyborohydride were added. After stirring another 1 h, an additional 0.145 g of 3-(2-oxo-1-piperidinyl)propanal and 0.3 g sodium triacetoxyborohydride were added and stirred at 0° C. for another ½ hour. The reaction was evaporated in vacuo and the residue was dissolved in CH2Cl2, washed with 2N Na2CO3, and back extracted the aqueous 2× with CH2Cl2. The organics were combined, washed with brine, dried over MgSO4, filtered and evaporated in vacuo. The residue was dissolved in CH2Cl2 and chromatographed on silica gel eluting with 10-100% acetone in hexanes to provide, after combining pure fractions and concentrating them in vacuo, the product as a clear viscous oil. 1H NMR (300 MHz, DMSO-d6) δ ppm 1.25-1.31 (m, 3 H), 1.63-1.77 (m, 6 H), 2.19 (t, J=5.90 Hz, 2 H), 3.12-3.25 (m, 4 H), 3.24-3.39 (m, 2 H), 3.94 (s, 2 H), 4.26 (q, J=7.11 Hz, 2 H), 7.08-7.16 (m, 3 H), 7.31 (ddd, J=12.00, 5.33, 3.02 Hz, 2 H), 7.61 (t, J=5.69 Hz, 1 H), 7.76 (d, J=1.82 Hz, 1 H); ES+ MS: 414 (M+H+).

Workup

  1. stirringAfter stirring another 1 h
  2. stirringstirred at 0° C. for another ½ hour
  3. customThe reaction was evaporated in vacuo
  4. dissolutionthe residue was dissolved in CH2Cl2
  5. washwashed with 2N Na2CO3
  6. extractionback extracted the aqueous 2× with CH2Cl2
  7. washwashed with brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customevaporated in vacuo
  11. dissolutionThe residue was dissolved in CH2Cl2
  12. customchromatographed on silica gel eluting with 10-100% acetone in hexanes
  13. customto provide
  14. concentrationconcentrating them in vacuo

Sources & evidence

ORD record
ord-6be4cb39fe4f4e1986a1a7b809c4e697
Source dataset
uspto-grants-2014_04
Patent number
US08691991B2

Reaction notes

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