Piperidine → Glu(OtBu)-Arg(Pmc)-Val-Asp(Allyl)-OBzl

HRID 414000Notes

Reaction equation

HRID 414000 reaction equation
[NH:1](C(OCC1C2C(=CC=CC=2)C2C1=CC=CC=2)=O)[C@H:2]([C:12]([NH:14][C@H:15]([C:41]([NH:43][C@H:44]([C:48]([NH:50][C@H:51]([C:59]([O:61][CH2:62][C:63]1[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=1)=[O:60])[CH2:52][C:53](=[O:58])[O:54][CH2:55][CH:56]=[CH2:57])=[O:49])[CH:45]([CH3:47])[CH3:46])=[O:42])[CH2:16][CH2:17][CH2:18][NH:19][C:20](=[NH:40])[NH:21][S:22]([C:25]1[C:38]([CH3:39])=[C:36]([CH3:37])[C:35]2[O:34][C:31]([CH3:33])([CH3:32])[CH2:30][CH2:29][C:28]=2[C:26]=1[CH3:27])(=[O:24])=[O:23])=[O:13])[CH2:3][CH2:4][C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:9])[CH3:8].N1CCCCC1>ClCCl.CCCCCCC>[NH2:1][C@H:2]([C:12]([NH:14][C@H:15]([C:41]([NH:43][C@H:44]([C:48]([NH:50][C@H:51]([C:59]([O:61][CH2:62][C:63]1[CH:64]=[CH:65][CH:66]=[CH:67][CH:68]=1)=[O:60])[CH2:52][C:53](=[O:58])[O:54][CH2:55][CH:56]=[CH2:57])=[O:49])[CH:45]([CH3:47])[CH3:46])=[O:42])[CH2:16][CH2:17][CH2:18][NH:19][C:20](=[NH:40])[NH:21][S:22]([C:25]1[C:38]([CH3:39])=[C:36]([CH3:37])[C:35]2[O:34][C:31]([CH3:33])([CH3:32])[CH2:30][CH2:29][C:28]=2[C:26]=1[CH3:27])(=[O:23])=[O:24])=[O:13])[CH2:3][CH2:4][C:5](=[O:11])[O:6][C:7]([CH3:8])([CH3:9])[CH3:10]

Participants

5

Reactant 2

HCID 8082PiperidineHCID 178459568Fmoc-Glu(OBut)-Arg(Pmc)-Val-Asp(Allyl)-OBzl

Product 1

HCID 178459569Glu(OtBu)-Arg(Pmc)-Val-Asp(Allyl)-OBzl

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8900HeptaneSolvent

Procedure

To a solution of Fmoc-Glu(OBut)-Arg(Pmc)-Val-Asp(OAllyl)-OBzl (SEQ ID NO: 37) (12.3 g, 10.3 mmol) in 105 mL of dichloromethane is added piperidine (3.5 g, 41.3 mmol) at ambient temperature. The mixture is stirred 2 hours, then diluted with heptane, concentrated to half volume, and left standing in the freezer overnight. The liquor is decanted from the oily residue, which is then taken up in dichloromethane. The solution is washed with 0.5M aqueous citric acid, water, and brine, dried (magnesium sulfate), filtered, and concentrated. The crude solid is triturated twice with heptane and filtered to give 9.0 g of Glu(OtBu)-(L)Arg(Pmc)-Val-Asp(OAllyl)-OBzl as a white powder. (Mcalc 970.2; M+1obsvd 971).

Workup

  1. concentrationconcentrated to half volume
  2. waitleft
  3. customstanding in the freezer overnight
  4. customThe liquor is decanted from the oily residue, which
  5. washThe solution is washed with 0.5M aqueous citric acid, water, and brine
  6. dry with materialdried (magnesium sulfate)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude solid is triturated twice with heptane
  10. filtrationfiltered

Sources & evidence

ORD record
ord-20a68893bed0432f9a3b3628f369c0f6
Source dataset
uspto-grants-2003_05
Patent number
US06569993B1

Reaction notes

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