Pyridine → HCID 131726471, compound

HRID 1354873Notes

Reaction equation

HRID 1354873 reaction equation
[NH:1]([C:36]([O:38][CH2:39][CH:40]=[CH2:41])=[O:37])[C@@H:2]([C:4]([NH:6][C@H:7]([C:18]([NH:20][C@H:21]([C:33]([OH:35])=[O:34])[CH2:22][CH2:23][CH2:24][CH2:25][NH:26][C:27]([O:29][CH2:30][CH:31]=[CH2:32])=[O:28])=[O:19])[CH2:8][C:9]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[NH:11][CH:10]=1)=[O:5])[CH3:3].[CH3:42][C:43]([NH:54][CH2:55][CH:56]([OH:72])[CH2:57][O:58][C:59]1[C:64]2[C:65]3[C:70]([NH:71][C:63]=2[CH:62]=[CH:61][CH:60]=1)=[CH:69][CH:68]=[CH:67][CH:66]=3)([C:45]1[CH:50]=[CH:49][C:48]([N:51]=[N+:52]=[N-:53])=[CH:47][CH:46]=1)[CH3:44].C1C(C(O)=O)=CC=C(N)C=1.N1C=CC=CC=1.C1C([N+]([O-])=O)=CC=C([Cl-]C([O-])=O)C=1>>[NH:1]([C:36]([O:38][CH2:39][CH:40]=[CH2:41])=[O:37])[C@@H:2]([C:4]([NH:6][C@H:7]([C:18]([NH:20][C@H:21]([C:33]([OH:35])=[O:34])[CH2:22][CH2:23][CH2:24][CH2:25][NH:26][C:27]([O:29][CH2:30][CH:31]=[CH2:32])=[O:28])=[O:19])[CH2:8][C:9]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[NH:11][CH:10]=1)=[O:5])[CH3:3].[CH3:44][C:43]([NH:54][CH2:55][CH:56]([OH:72])[CH2:57][O:58][C:59]1[C:64]2[C:65]3[C:70]([NH:71][C:63]=2[CH:62]=[CH:61][CH:60]=1)=[CH:69][CH:68]=[CH:67][CH:66]=3)([C:45]1[CH:50]=[CH:49][C:48]([N:51]=[N+:52]=[N-:53])=[CH:47][CH:46]=1)[CH3:42].[CH3:44][C:43]([NH:54][CH2:55][CH:56]([OH:72])[CH2:57][O:58][C:59]1[C:64]2[C:65]3[C:70]([NH:71][C:63]=2[CH:62]=[CH:61][CH:60]=1)=[CH:69][CH:68]=[CH:67][CH:66]=3)([C:45]1[CH:50]=[CH:49][C:48]([N:51]=[N+:52]=[N-:53])=[CH:47][CH:46]=1)[CH3:42]

Participants

3

Reactant 2

HCID 1049PyridineHCID 131726472HCID 131726472, compound

Product 1

HCID 131726471HCID 131726471, compoundYield 90.6%

Procedure

A solution of 70 mg (85 μmol) of compound 30, pyridine (17 μl, 2.5 equiv) and 4-nitrophenylchloroformate (34 mg, 2.0 equiv) was stirred under an Argon atmosphere at 0° C. for two hours and for 24 hours at room temperature. The solution was evaporated in vacuo and the residual product was dissolved in chloroform. After washing the organic layer with brine and 0.5 N potassium bisulfate, the organic layer was dried over anhydrous sodium sulfate and concentrated to dryness. The resulting crude product was subjected to column chromatography (SiO2—CHCl3/MeOH 20/1) to obtain 54 mg (64%) of 31 as a pale yellow solid. 1H-NMR (300 MHz, CDCl3/CD3OD): δ 0.90–2.10 (m, 9H, CH3-Ala and 3 CH2-Lys), 2.90–3.10 (m, 4H, N—CH2-Lys and CH2-Trp), 3.27 (bd, 1H, benzylic), 4.35–4.78 (m, 6H, 2Hα and Aloc), 4.90–5.52 (m, 4H, Aloc), 5.13 (s, 2H, benzylic-spacer), 5.60 (m, 1H, Aloc), 5.94 (m, 1H, Aloc), 7.10–7.46 (m, 15H, aromatic), 8.36 (d, 2H, aromatic-PNP) ppm; MS (FAB) m/e 991 (M+H)+, 1013 (M+Na)+; C50H54N54N8O14.¾H2O) calculated C 59.78%; H, 5.57 %; N, 11.15%; measured C, 60.12%; H, 5.89%; N, 10.76%.

Workup

  1. customThe solution was evaporated in vacuo
  2. dissolutionthe residual product was dissolved in chloroform
  3. washAfter washing the organic layer with brine and 0.5 N potassium bisulfate
  4. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  5. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-933abd7cdc824521be8b71d379c5b8ec
Source dataset
uspto-grants-2007_05
Patent number
US07223837B2

Reaction notes

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