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Toluene → (3R,4R)-benzyl 3-(((2S,6R)-N-((R)-1-(1-benzyl-3-(2,5-difluorophenyl)-1H-1,2,4-triazol-5-yl)-2,2-dimethylpropyl)-2,6-dimethylmorpholine-4-carboxamido)methyl)-4-fluoropyrrolidine-1-carboxylate

HRID 1037486
Notes
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Reaction equation

HRID 1037486 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[C:9]1[N:13]=[C:12]([C@H:14]([NH:19][CH2:20][C@H:21]2[C@@H:25]([F:26])[CH2:24][N:23]([C:27]([O:29][CH2:30][C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)=[O:28])[CH2:22]2)[C:15]([CH3:18])([CH3:17])[CH3:16])[N:11]([CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[C:40](F)[CH:39]=2)[N:10]=1.C(N(CC)CC)C.C(Cl)(Cl)=[O:53].C1(C)C=CC=CC=1.C(N1C([C@H:75]([N:80]([CH2:84][C@H:85]2[C@@H:89](F)CN(C(OCC3C=CC=CC=3)=O)C2)[C:81](Cl)=[O:82])[C:76](C)(C)[CH3:77])=NC(C2C=C(F)C=CC=2F)=N1)C1C=CC=CC=1.CC1OC(C)CNC1>ClCCl>[CH2:37]([N:11]1[C:12]([C@H:14]([N:19]([CH2:20][C@H:21]2[C@@H:25]([F:26])[CH2:24][N:23]([C:27]([O:29][CH2:30][C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)=[O:28])[CH2:22]2)[C:81]([N:80]2[CH2:84][C@@H:85]([CH3:89])[O:53][C@@H:76]([CH3:77])[CH2:75]2)=[O:82])[C:15]([CH3:18])([CH3:16])[CH3:17])=[N:13][C:9]([C:3]2[CH:4]=[C:5]([F:8])[CH:6]=[CH:7][C:2]=2[F:1])=[N:10]1)[C:38]1[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 6

HCID 1140TolueneHCID 6371PhosgeneHCID 8471TriethylamineHCID 1108622,6-DimethylmorpholineHCID 58473029(3R,4R)-benzyl 3-(((R)-1-(3-(2,5-difluorophenyl)-1-(3-fluorobenzyl)-1H-1,2,4-triazol-5-yl)-2,2-dimethylpropylamino)methyl)-4-fluoropyrrolidine-1-carboxylate
HCID 58473056
(3S,4R)-benzyl 3-((((R)-1-(1-benzyl-3-(2,5-difluorophenyl)-1H-1,2,4-triazol-5-yl)-2,2-dimethylpropyl)(chlorocarbonyl)amino)methyl)-4-fluoropyrrolidine-1-carboxylate

Product 1

HCID 58473031(3R,4R)-benzyl 3-(((2S,6R)-N-((R)-1-(1-benzyl-3-(2,5-difluorophenyl)-1H-1,2,4-triazol-5-yl)-2,2-dimethylpropyl)-2,6-dimethylmorpholine-4-carboxamido)methyl)-4-fluoropyrrolidine-1-carboxylateYield 66.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

To a solution of (3R,4R)-benzyl 3-(((R)-1-(3-(2,5-difluorophenyl)-1-(3-fluorobenzyl)-1H-1,2,4-triazol-5-yl)-2,2-dimethylpropylamino)methyl)-4-fluoropyrrolidine-1-carboxylate (110 mg, 0.186 mmol) in dichloromethane (1.9 mL, 0.1 M solution) was added triethylamine (78 μL, 0.558 mmol) followed by addition of 20% phosgene in toluene (66 mg, 0.223 mmol) at room temperature. After the resulting solution was stirred at room temperature for 15 min (LC/MS (uplc): MH+654.3, 1.37 min for (3S,4R)-benzyl 3-((((R)-1-(1-benzyl-3-(2,5-difluorophenyl)-1H-1,2,4-triazol-5-yl)-2,2-dimethylpropyl)(chlorocarbonyl)amino)methyl)-4-fluoropyrrolidine-1-carboxylate), 2,6-dimethylmorpholine (64 mg, 0.558 mmol) was added and heat at 40° C. for overnight (in a seal tube). The reaction mixture was quenched with H2O and extracted with EtOAc. The organic layer was washed with NaHCO3 solution and brine, dried over anhydrous sodium sulfate, filtered and concentrated. After the volatile organic materials were removed in vacuo, the crude product was purified on preparative reverse phase HPLC. The combined fractions of the product were neutralized with saturated NaHCO3 solution, which was then extracted with EtOAc. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to yield the desired (3R,4R)-benzyl 3-(((2S,6R)—N—((R)-1-(1-benzyl-3-(2,5-difluorophenyl)-1H-1,2,4-triazol-5-yl)-2,2-dimethylpropyl)-2,6-dimethylmorpholine-4-carboxamido)methyl)-4-fluoropyrrolidine-1-carboxylate (91 mg, 66.7%, over 2 steps). LC/MS (uplc): MH+733.5, 1.41 min.

Workup

  1. additionwas added
  2. customThe reaction mixture was quenched with H2O
  3. extractionextracted with EtOAc
  4. washThe organic layer was washed with NaHCO3 solution and brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customAfter the volatile organic materials were removed in vacuo
  9. customthe crude product was purified on preparative reverse phase HPLC
  10. extractionwas then extracted with EtOAc
  11. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-9d45bfdb723e477ba82a5a83b6ee9bc5
Source dataset
uspto-grants-2013_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08546434B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes