7,12-Dimethylbenz(a)anthracene → 1-[2-(3,5-Dichloro-4-hydroxy-benzoylamino)-propionyl]-pyrrolidine-2-carboxylic acid (2-benzyloxy-5-oxo-tetrahydro-furan-3-yl)-amide

HRID 1861254

Reaktionsgleichung

Reaktionsgleichung von HRID 1861254
[CH2:1]([O:8][CH:9]1[CH:13]([NH:14][C:15]([CH:17]2[CH2:21][CH2:20][CH2:19][N:18]2[C:22](=[O:40])[CH:23]([NH:25][C:26](=[O:39])[C:27]2[CH:32]=[C:31]([Cl:33])[C:30]([O:34]CC=C)=[C:29]([Cl:38])[CH:28]=2)[CH3:24])=[O:16])[CH2:12][C:11](=[O:41])[O:10]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC1C2C(=CC=CC=2)C(C)=C2C=1C=CC1C2=CC=CC=1>C(Cl)Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([O:8][CH:9]1[CH:13]([NH:14][C:15]([CH:17]2[CH2:21][CH2:20][CH2:19][N:18]2[C:22](=[O:40])[CH:23]([NH:25][C:26](=[O:39])[C:27]2[CH:32]=[C:31]([Cl:33])[C:30]([OH:34])=[C:29]([Cl:38])[CH:28]=2)[CH3:24])=[O:16])[CH2:12][C:11](=[O:41])[O:10]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

5

Edukt 2

HCID 60017,12-Dimethylbenz(a)anthraceneHCID 229774861-[2-(4-Allyloxy-3,5-dichloro-benzoylamino)-propionyl]-pyrrolidine-2-carboxylic acid (2-benzyloxy-5-oxo-tetrahydro-furan-3-yl)-amide

Produkt 1

HCID 229777651-[2-(3,5-Dichloro-4-hydroxy-benzoylamino)-propionyl]-pyrrolidine-2-carboxylic acid (2-benzyloxy-5-oxo-tetrahydro-furan-3-yl)-amideAusbeute 71,8 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A 140 mg sample of 82 (0.23 mmol) was dissolved in CH2Cl2 (4 mL) and treated with DMBA (35.4 mg, 0.26 mmol) and Pd(PPh3)4 (32 mg, 0.028 mmol). The solution was stirred at 0° C. for 15 mins, warmed to room temperature for 2 hours, then diluted with CH2Cl2 and washed with water (2×) and brine. The solvent was concentrated in vacuo and the residue purified by flash chromatography on silica gel using MeOH/CH2Cl2 (1/99 to 3/97) to give the title compound (93.2 mg, 71% yield). 1H-NMR (500 MHz, CD3OD) δ 1.16 (d, 0.25H), 1.28-1.49 (m, 2.75H), 1.63-2.33 (m, 4H), 2.48 (dd, 0.4H), 3.39-3.59 (m, 0.2H), 3.60-3.73 (m, 0.8H), 3.73-3.96 (m, 1H), 4.24-4.48 (m, 2H), 4.57-4.92 (m, 7H), 5.44 (s, 0.4H), 5.50 (d, 0.4H), 5.64 (d, 0.8H), 5.75 (d, 0.5H), 7.16-7.43 (m, 5H), 7.78-7.89 (m, 1.6H), 8.40-8.63 (m, 0.4H). Analytical HPLC (cyano column) (mixture of 2 diastereomers) 11.57, 11.82 min. LC-MS (ES+) m/e=564.1 (M+H).

Aufarbeitung

  1. temperaturewarmed to room temperature for 2 hours
  2. washwashed with water (2×) and brine
  3. concentrationThe solvent was concentrated in vacuo
  4. customthe residue purified by flash chromatography on silica gel

Quellen und Nachweise

ORD-Eintrag
ord-3155e3f9dcbf4d94a261c7938d49d465
Quelldatensatz
uspto-grants-2003_03
Patentnummer
US06531474B1

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