Acetic Acid → {Benzyloxycarbonyl-[2-(1,3-dioxo-1,3-dihydro-isoindol-2-ylamino)-ethyl]-amino}-acetic acid ethyl ester

HRID 2381922Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2381922
[CH2:1]([O:3][C:4](=[O:31])[CH2:5][N:6]([C:21]([O:23][CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)=[O:22])[CH2:7]/[CH:8]=[N:9]/[N:10]1[C:18](=[O:19])[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11]1=[O:20])[CH3:2].C([BH3-])#N.[Na+].C(O)(=O)C>CC#N.CCOC(C)=O>[CH2:1]([O:3][C:4](=[O:31])[CH2:5][N:6]([C:21]([O:23][CH2:24][C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1)=[O:22])[CH2:7][CH2:8][NH:9][N:10]1[C:18](=[O:19])[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11]1=[O:20])[CH3:2]

Komponenten

6

Edukt 3

HCID 176Acetic AcidHCID 5003444Sodium cyanoborohydrideHCID 87496342ethyl 2-[[(2E)-2-(1,3-dioxoisoindol-2-yl)iminoethyl]-phenylmethoxycarbonylamino]acetate

Produkt 1

HCID 68557343{Benzyloxycarbonyl-[2-(1,3-dioxo-1,3-dihydro-isoindol-2-ylamino)-ethyl]-amino}-acetic acid ethyl esterAusbeute 81,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6342AcetonitrileLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A solution of (benzyloxycarbonyl-{2-[(E)-1,3-dioxo-1,3-dihydro-isoindol-2-ylimino]ethyl}-amino)-acetic acid ethyl ester (7.7 mmol) in CH3CN (65 mL) is treated with sodium cyanoborohydride (1.92 g, 30.5 mmol), and acetic acid (6.8 mL, 118.8 mmol) is added with stirring under N2. After 5.5 h, the reaction solution is diluted with EtOAc (150 mL) and washed with saturated aqueous KHCO3 (3×50 mL) and saturated aqueous NaCl (50 mL). The organic phase is dried (MgSO4), filtered, and concentrated in vacuo. The residue is purified by silica gel chromatography (75:25 to 50:50 heptane:ethyl acetate gradient elution) to afford {benzyloxycarbonyl-[2-(1,3-dioxo-1,3-dihydro-isoindol-2-ylamino)-ethyl]-amino}-acetic acid ethyl ester as an oil (2.66 g, 81%). MS: 426 (M+H); 1H NMR (300 MHz, CDCl3) δ 7.79-7.91 (m, 2H), 7.69-7.79 (m, 2H), 7.17-7.39 (m, 5H), 5.04-5.21 (m, 2H), 4.87-5.04 (m, 1H), 4.04-4.23 (m, 4H), 3.48-3.59 (m, 2H), 3.18-3.38 (m, 2H), 1.10-1.30 (m, 3H).

Aufarbeitung

  1. additionis added
  2. washwashed with saturated aqueous KHCO3 (3×50 mL) and saturated aqueous NaCl (50 mL)
  3. dry with materialThe organic phase is dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue is purified by silica gel chromatography (75:25 to 50:50 heptane:ethyl acetate gradient elution)

Quellen und Nachweise

ORD-Eintrag
ord-110ae9cb1f6243f985e93cca7577e535
Quelldatensatz
uspto-grants-2012_09
Patentnummer
US08258130B2

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