StartseiteMCPWorkbenchSkills
StartseiteWorkbenchBenachrichtigungenMein Bereich
llms.txt · MCP-AnleitungDatenschutz · Nutzungsbedingungen · Supportv1.8.0
  1. Startseite
  2. /Reaktion

7,13-Diacetylbaccatin III → 2-Debenzoyl-7,13-diacetylbaccatin III

HRID 859837
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 859837
[H-].COCCO[Al+]OCCOC.[CH3:13][C:14]1[C@@H:31]([O:32][C:33]([CH3:35])=[O:34])[CH2:30][C@:26]2([OH:36])[C:27]([CH3:29])([CH3:28])[C:15]=1[C@@H:16]([O:57][C:58]([CH3:60])=[O:59])[C:17]([C@@:19]1([CH3:56])[C@H:24]([C@@H:25]2[O:37]C(C2C=CC=CC=2)=O)[C@:23]2([O:48][C:49]([CH3:51])=[O:50])[CH2:46][O:47][C@@H:22]2[CH2:21][C@@H:20]1[O:52][C:53]([CH3:55])=[O:54])=[O:18]>C1COCC1>[CH3:13][C:14]1[C@@H:31]([O:32][C:33]([CH3:35])=[O:34])[CH2:30][C@:26]2([OH:36])[C:27]([CH3:28])([CH3:29])[C:15]=1[C@@H:16]([O:57][C:58]([CH3:60])=[O:59])[C:17]([C@@:19]1([CH3:56])[C@H:24]([C@@H:25]2[OH:37])[C@:23]2([O:48][C:49]([CH3:51])=[O:50])[CH2:46][O:47][C@@H:22]2[CH2:21][C@@H:20]1[O:52][C:53]([CH3:55])=[O:54])=[O:18]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

4

Edukt 2

HCID 109743987,13-Diacetylbaccatin IIIHCID 22591236Bis(2-methoxyethoxy) aluminum hydride

Produkt 1

HCID 1010996262-Debenzoyl-7,13-diacetylbaccatin IIIAusbeute 42 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Bis(2-methoxyethoxy)-aluminum hydride (65+ wt % in toluene, 3 equiv.) was added dropwise to a stirred solution of 7,13-diacetylbaccatin III (170 mg, 253 μmol) in dry THF (2 mL) at 0° C. After stirring for 30 minutes at 0° C., the reaction was quenched by dropwise addition of saturated NH4Cl. The mixture was stirred for 10 minutes, then warmed to room temperature and diluted with EtOAc (50 mL), followed by addition of water (10 mL). The aqueous phase was separated and extracted again with EtOAc (2×25 mL). The combined organic fractions were washed with brine and water, then dried over anhydrous MgSO4. The solvent was evaporated and the crude product was purified by silica gel flash column chromatography (40–60% EtOAc gradient in hexane) to yield 2-debenzoyl-7,13-diacetylbaccatin III (see FIG. 11) (60 mg, 42% yield, 99% purity by 1H-NMR). 1H-NMR (300 MHz, CDCl3)δ: 1.04 (s, CH3), 1.22 (s, CH3), 1.77 (s, CH3), 1.85 (ddd, J=1.8, 10.8, and 14.4 Hz, H-6β), 1.90 (d, J=1.2 Hz, vinyl-CH3), 2.02 (s, C(O)CH3), 2.14 (s, C(O)CH3), 2.15 (s, C(O)CH3), 2.20 (s, C(O)CH3), 2.58 (ddd, J=7.2, 9.6, and 14.4 Hz, H-6α), 2.65 (d, J=5.1 Hz, OH at C-2), 3.58 (d, J=6.9 Hz, H-3), 3.90 (dd, J=5.4 and 6.5 Hz, H-2), 4.49 (d, J=9.6 Hz, H-20α), 4.63 (d, J=9.6 Hz, H-20β), 4.97 (dd, J=1.8 and 9.6 Hz, H-5), 5.55 (dd, J=7.2 and 10.7 Hz, H-7), 6.15 (dt, J=1.2 and 9.6 Hz, H-13), 6.18 (s, H-10), H-14 proton signal obscured. APCI-MS: m/z 567 (PH+)

Aufarbeitung

  1. customthe reaction was quenched by dropwise addition of saturated NH4Cl
  2. stirringThe mixture was stirred for 10 minutes
  3. temperaturewarmed to room temperature
  4. additiondiluted with EtOAc (50 mL)
  5. additionfollowed by addition of water (10 mL)
  6. customThe aqueous phase was separated
  7. extractionextracted again with EtOAc (2×25 mL)
  8. washThe combined organic fractions were washed with brine and water
  9. dry with materialdried over anhydrous MgSO4
  10. customThe solvent was evaporated
  11. customthe crude product was purified by silica gel flash column chromatography (40–60% EtOAc gradient in hexane)

Quellen und Nachweise

ORD-Eintrag
ord-f8de524c9c714efe9ef4c12971fa0fda
Quelldatensatz
uspto-grants-2006_12
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07153676B1

Notizen zur Reaktion

Wird geladen…

Auf dieser SeiteKomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion