Formaldehyde → Diallylacetic Acid Ethyl Ester

HRID 1699969

Reaktionsgleichung

Reaktionsgleichung von HRID 1699969
[CH2:1]([C:4]([CH2:15][CH:16]=[CH2:17])(C(OCC)=O)[C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH:2]=[CH2:3].C(C(CC=C)CC=C)(OCC)=O.C(O[C@H]1C[C@@H](CO[C:41](=[O:43])[CH3:42])C=C1)(=O)C.C1CC=CC=1.C=O.[F:51][C:52]1[C:53]([NH2:59])=[N:54][C:55](=[O:58])[NH:56][CH:57]=1.C(OC1C=CC([N+]([O-])=O)=CC=1)(=O)C>C(O)(=O)C>[C:5]([CH:4]([CH2:1][CH:2]=[CH2:3])[CH2:15][CH:16]=[CH2:17])([O:7][CH2:8][CH3:9])=[O:6].[C:41]([NH:59][C:53]1[C:52]([F:51])=[CH:57][NH:56][C:55](=[O:58])[N:54]=1)(=[O:43])[CH3:42]

Komponenten

10

Edukt 7

HCID 712FormaldehydeHCID 7612CyclopentadieneHCID 132434-Nitrophenyl AcetateHCID 76664Diethyl diallylmalonateHCID 10877522Diallylacetic Acid Ethyl EsterHCID 69459408cis-(+/-)-3-Acetoxy-5-(acetoxymethyl)cyclopenteneHCID 178509021HCID 178509021, Verbindung

Produkt 2

HCID 10877522Diallylacetic Acid Ethyl EsterAusbeute 78 %HCID 178474477HCID 178474477, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Versuchsvorschrift

Synthesis of cis-(±)-Carbocyclic d4 Cytosine Nucleosides and their 5′-Triphosphates Referring to Scheme 11, starting from diethyl diallylmalonate (701), the 4-carbethoxy-1,6-heptadiene (702) was synthesized in 78% yield (W. A. Nugent, J. Am. Chem. Soc., 1995, 117, 8992-8998). Compound 703 was synthesized from compound 702 in 71% yield (L. E. Martinez, J. Org. Chem., 1996, 61, 7963-7966), and compound 705 was synthesized from compound 704 in 43% yield (D. M. Hodgson, J. Chem. Soc. Perkin Trans. I, 1994, 3373-3378). The key intermediate cis-(±)-3-acetoxy-5-(acetoxymethyl)cyclopentene (708) can be alternatively synthesized from cyclopentadiene and formaldehyde in acetic acid using a Prins reaction (E. A. Saville-Stones, J. Chem. Soc. Perkin Trans. I, 1991, 2603-2604) albeit it suffers low yield and inseparable problems; or from a bicyclic lactone which was synthesized by multiple steps through 4 steps (F. Burlina, Bioorg. Med. Chem. Lett., 1997, 7, 247-250). The latter methodology gave a chiral 708 [(−)-enantiomer], although it needed to synthesized a chiral bicyclic lactone. N4-Acetyl-5-fluorocytosine was synthesized from 5-fluorocytosine and p-nitrophenyl acetate (A. S. Steinfeld, J. Chem. Research (M), 1979, 1437-1450).

Aufarbeitung

  1. customa Prins reaction (E
  2. customI, 1991, 2603-2604) albeit it suffers low yield
  3. customThe latter methodology gave a chiral 708 [(−)-enantiomer]

Quellen und Nachweise

ORD-Eintrag
ord-9b37b9daf9c74b198ff108b5c831eb61
Quelldatensatz
uspto-grants-2002_02
Patentnummer
US06348587B1

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