Iodine → Tetrahydro-2-(17-acetoxyheptadecyloxy)-2H-pyran

HRID 910815

Reaktionsgleichung

Reaktionsgleichung von HRID 910815
II.[C:3]([O:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17]Br)(=[O:5])[CH3:4].C(COC)OC.CC([C@H]1N=C(C2C=CC=C(C3OC[C@@H](C(C)C)N=3)N=2)OC1)C.CC([C@@H]1N=C(C2C=CC=C(C3OC[C@H](C(C)C)N=3)N=2)OC1)C.I[CH2:70][CH2:71][CH2:72][CH2:73][CH2:74][CH2:75][O:76][CH:77]1[CH2:82][CH2:81][CH2:80][CH2:79][O:78]1>CN1C(=O)N(C)CC1.C1COCC1.[Zn].Cl[Ni]Cl>[C:3]([O:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:70][CH2:71][CH2:72][CH2:73][CH2:74][CH2:75][O:76][CH:77]1[CH2:82][CH2:81][CH2:80][CH2:79][O:78]1)(=[O:5])[CH3:4]

Komponenten

11

Edukt 6

HCID 807Iodine2×HCID 80711,2-DimethoxyethaneHCID 688211(S,S)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridineHCID 688213(R,R)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridineHCID 501616211-Bromoundecyl acetateHCID 110560482H-Pyran, tetrahydro-2-[(6-iodohexyl)oxy]-

Produkt 1

HCID 57548717Tetrahydro-2-(17-acetoxyheptadecyloxy)-2H-pyran

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 23994ZincKatalysator2×HCID 24385Nickel DichlorideKatalysatorHCID 66611,3-Dimethyl-2-imidazolidinoneLösungsmittel2×HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

In a 10-ml Schlenk tube, zinc powder (98 mg, 1.5 mmol) was dried at 70° C. under high vacuum for 30 min. After back-filling with nitrogen, DMI (1 ml) and iodine (13 mg, 0.05 mmol) were added. The mixture was stirred until disappearance of the iodine color, after which neat 11-bromoundecyl acetate (293 mg, 1 mmol) was added. The tube was sealed, and the mixture was stirred at 70° C. for 12 h, cooled to the room temperature and zinc excess was allowed to settle. In a 5-ml flask, NiCl2.glyme (17 mg, 0.08 mmol) and (R)-(i-Pr)-Pybox (or (S)-(i-Pr)-Pybox) (30 mg, 0.1 mmol) were dissolved in DMI (1 ml) and THF (0.3 ml), then neat I(CH2)6OTHP 38 (240 mg, 0.77 mmol) was added followed by addition of the organozinc solution 33 via cannula. Reaction mixture was stirred at room temperature for 14 h, quenched with NH4Cl and extracted with EtOAc. Extract was dried over Na2SO4 and concentrated by solvent evaporation. Chromatography in hexane-ethyl ether (15:1, 10:1) gave the product, 212 mg (69%).

Aufarbeitung

  1. customThe tube was sealed
  2. customReaction mixture
  3. stirringwas stirred at room temperature for 14 h
  4. customquenched with NH4Cl
  5. extractionextracted with EtOAc
  6. extractionExtract
  7. dry with materialwas dried over Na2SO4
  8. concentrationconcentrated by solvent evaporation
  9. customChromatography in hexane-ethyl ether (15:1, 10:1) gave the product, 212 mg (69%)

Quellen und Nachweise

ORD-Eintrag
ord-7af92b87e3a04b2bae80dff7a520083a
Quelldatensatz
uspto-grants-2011_09
Patentnummer
US08022235B2

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