Ethyl 11-bromoundecanoate → Ethyl 17-(tetrahydropyran-2-yl-oxy)-heptadecanoate

HRID 1367722Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1367722
I[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][O:8][CH:9]1[CH2:14][CH2:13][CH2:12][CH2:11][O:10]1.Br[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27].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.CC(N(C)C)=O.C1COCC1.[Zn].Cl[Ni]Cl.C(COC)OC.IC1C=CC(CCCCCCCCCCCCCCCCCCO)=CC=1>[O:10]1[CH2:11][CH2:12][CH2:13][CH2:14][CH:9]1[O:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27]

Komponenten

10

Edukt 3

HCID 235144Ethyl 11-bromoundecanoateHCID 688211(S,S)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridineHCID 110560482H-Pyran, tetrahydro-2-[(6-iodohexyl)oxy]-2×

Produkt 1

HCID 66970149Ethyl 17-(tetrahydropyran-2-yl-oxy)-heptadecanoateAusbeute 71 %

Reagenzien, Katalysatoren, Lösungsmittel 6

HCID 23994ZincKatalysatorHCID 1165580418-(p-Iodophenyl)octadecanolKatalysatorHCID 15773433Dichloronickel;1,2-dimethoxyethaneKatalysatorHCID 8028TetrahydrofuranLösungsmittelHCID 31374DimethylacetamideLösungsmittel2×HCID 688213(R,R)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridineLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

From (38) and (76). Zinc powder (166 mg, 2.55 mmol) was dried at 70° C. for 30 min in a sealed tube, then DMA (2.5 ml) and solid 12 (22 mg, 0.09 mmol) were added. After stirring for 10 min, neat ethyl 11-bromoundecanoate (500 mg, 1.7 mmol) was added and the reaction mixture was stirred in the sealed tube for 10 h at 80° C. In a 10-ml flask, NiCl2-glyme (29 mg, 0.13 mmol) and (R)-(i-Pr)-Pybox (or (S)-(i-Pr)-Pybox) (51 mg, 0.17 mmol) were dissolved in DMA (1.5 ml) and THF (0.5 ml), then neat I(CH2)6OTHP 38 (410 mg, 1.31 mmol) was added. This mixture was cooled to 0° C. and organozinc solution 76 was added via cannula. The reaction mixture was allowed to warm to the room temperature over period of 12 h and stirred at room temperature for additional 12 h. The reaction was quenched by addition of aqueous NH4Cl, extracted with EtOAc, the extract was dried over Na2SO4 and evaporated. The crude product was purified by silica gel chromatography in hexane-EtOAc (98:2, 97:3, 96:4) to afford the product ethyl 17-(tetrahydropyran-2-yl-oxy)-heptadecanoate 78 (369 mg, 71%).

Aufarbeitung

  1. stirringthe reaction mixture was stirred in the sealed tube for 10 h at 80° C
  2. temperatureto warm to the room temperature over period of 12 h
  3. stirringstirred at room temperature for additional 12 h
  4. customThe reaction was quenched by addition of aqueous NH4Cl
  5. extractionextracted with EtOAc
  6. dry with materialthe extract was dried over Na2SO4
  7. customevaporated
  8. customThe crude product was purified by silica gel chromatography in hexane-EtOAc (98:2, 97:3, 96:4)

Quellen und Nachweise

ORD-Eintrag
ord-44568b68e24e42b58d6440df7ef736cc
Quelldatensatz
uspto-grants-2011_02
Patentnummer
US07893286B2

Notizen zur Reaktion

Wird geladen…