Ammonium formate → HCID 118000708, compound

HRID 1470901Notes

Reaction equation

HRID 1470901 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][O:5][CH2:6][CH2:7][O:8][CH2:9][CH2:10][O:11][CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][O:20][CH2:21][CH2:22][O:23][CH2:24][CH2:25][CH2:26][NH:27][C:28]1[C:29]([C:77]([NH:79][C@H:80]([CH2:91][OH:92])[C:81]([O:83]CC2C=CC=CC=2)=[O:82])=[O:78])=[N:30][C:31]([NH:50][CH2:51][CH2:52][CH2:53][O:54][CH2:55][CH2:56][O:57][CH2:58][CH2:59][O:60][CH2:61][CH2:62][O:63][CH2:64][CH2:65][O:66][CH2:67][CH2:68][O:69][CH2:70][CH2:71][O:72][CH2:73][CH2:74][O:75][CH3:76])=[C:32]([C:34]([NH:36][C@H:37]([CH2:48][OH:49])[C:38](=[O:47])[O:39]CC2C=CC=CC=2)=[O:35])[N:33]=1.C([O-])=O.[NH4+]>CO.O.[Pd]>[CH3:76][O:75][CH2:74][CH2:73][O:72][CH2:71][CH2:70][O:69][CH2:68][CH2:67][O:66][CH2:65][CH2:64][O:63][CH2:62][CH2:61][O:60][CH2:59][CH2:58][O:57][CH2:56][CH2:55][O:54][CH2:53][CH2:52][CH2:51][NH:50][C:31]1[C:32]([C:34]([NH:36][C@@H:37]([C:38]([OH:47])=[O:39])[CH2:48][OH:49])=[O:35])=[N:33][C:28]([NH:27][CH2:26][CH2:25][CH2:24][O:23][CH2:22][CH2:21][O:20][CH2:19][CH2:18][O:17][CH2:16][CH2:15][O:14][CH2:13][CH2:12][O:11][CH2:10][CH2:9][O:8][CH2:7][CH2:6][O:5][CH2:4][CH2:3][O:2][CH3:1])=[C:29]([C:77]([NH:79][C@@H:80]([C:81]([OH:83])=[O:82])[CH2:91][OH:92])=[O:78])[N:30]=1

Participants

6

Reactant 2

HCID 2723923Ammonium formate2×HCID 90255641HCID 90255641, compound

Product 1

HCID 118000708HCID 118000708, compoundYield 89.1%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalyst2×HCID 887MethanolSolventHCID 962WaterSolvent2×

Conditions

Temperature
60 °C

Procedure

A 250 mL round-bottom flask equipped with magnetic stir bar was charged with the above bis-benzyl ester 10 (0.390 g, 0.297 mmol) and ammonium formate (0.112 g, 1.78 mmol) in MeOH (10 mL) and water (10 mL). To this was added slurry of 10% Pd/C (0.095 g) in water (10 mL) and reaction mixture was stirred at 60° C. RP-LC/MS analysis after 1 h showed ˜60% mono-ester and the rest starting material. At this stage, additional ammonium formate (0.112 g, 1.78 mmol) and 10% Pd/C (0.095 g) were added and the reaction was completed in an hour. The catalyst was removed by filtration through Celite, washed with deionized water (˜100 mL), and the combined filtrates were concentrated in vacuo. The crude product was purified by preparative HPLC and the product was concentrated in vacuo and transferred into a 4 dram vial with acetonitrile, concentrated and vacuum dried to afford 8 (0.300 g, 76%) as red oil: HRMS (ESI) m/z calculated for C48H89N6O24 (M+H)+ 1133.5923, found 1133.5958.

Workup

  1. customA 250 mL round-bottom flask equipped with magnetic stir bar
  2. additionTo this was added
  3. waitthe reaction was completed in an hour
  4. customThe catalyst was removed by filtration through Celite
  5. washwashed with deionized water (˜100 mL)
  6. concentrationthe combined filtrates were concentrated in vacuo
  7. customThe crude product was purified by preparative HPLC
  8. concentrationthe product was concentrated in vacuo
  9. concentrationconcentrated
  10. customvacuum dried

Sources & evidence

ORD record
ord-c219ebe7eb3f4919bb7dbbb93b8ea0ac
Source dataset
uspto-grants-2015_04
Patent number
US09005581B2

Reaction notes

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