Ingenol → (4S,5R,6R,18R)-4,5-dihydroxy-3,8,8,15,15,18-hexamethyl-7,9-dioxapentacyclo[11.5.1.01,5.06,11.014,16]nonadeca-2,11-dien-19-one

HRID 2224676Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2224676
[CH3:1][C@H:2]1[C@:14]23[CH:17]=[C:18]([CH3:21])[C@H:19]([OH:20])[C@@:13]2([OH:22])[C@H:12]([OH:23])[C:11]([CH2:24][OH:25])=[CH:10][C@H:9]([C:15]3=[O:16])[C@@H:5]2[C:6]([CH3:8])([CH3:7])[C@@H:4]2[CH2:3]1.O.[C:27]1(C)[CH:32]=CC(S(O)(=O)=O)=C[CH:28]=1>CC(C)=O>[CH3:1][C@H:2]1[C:14]23[CH:17]=[C:18]([CH3:21])[C@H:19]([OH:20])[C@@:13]2([OH:22])[C@H:12]2[C:11]([CH2:24][O:25][C:27]([CH3:32])([CH3:28])[O:23]2)=[CH:10][CH:9]([C:15]3=[O:16])[CH:5]2[C:6]([CH3:8])([CH3:7])[CH:4]2[CH2:3]1

Komponenten

4

Edukt 2

HCID 442042IngenolHCID 521998p-Toluenesulfonic acid monohydrate

Produkt 1

HCID 91827745(4S,5R,6R,18R)-4,5-dihydroxy-3,8,8,15,15,18-hexamethyl-7,9-dioxapentacyclo[11.5.1.01,5.06,11.014,16]nonadeca-2,11-dien-19-one

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 180AcetoneLösungsmittel

Versuchsvorschrift

Ingenol is reacted with p-toluenesulphonic acid hydrate and acetone to give ingenol-5,20-acetonide according to the procedure of Opferkuch et al. (1981). Ingenol-5,20-acetonide is converted to the ingenol 3-acylate by treatment with the appropriate acyl chloride and 4-(N,N-dimethylamino)pyridine or pyridine in toluene or benzene, or treatment with the appropriate acid, an alkylpyridinium salt and tributylamine in toluene then treatment with methanolic perchloric acid according to the procedure of Sorg et al. (1982). The ingenol 3-acylate could be converted to the 20-chloro-20-deoxyingenol 3-acylate 5-benzoate by the method of Example 15.

Quellen und Nachweise

ORD-Eintrag
ord-74b874e03e8946aeac0449164807c659
Quelldatensatz
uspto-grants-2008_05
Patentnummer
US07378445B2

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