Formaldehyde → (3aR,6aR)-5-methyl-1-[(1R)-1-phenylethyl]-2,3,3a,4,6,6a-hexahydropyrrolo[3,2-c]pyrrole

HRID 1842701

Reaktionsgleichung

Reaktionsgleichung von HRID 1842701
[CH2:1]=O.[C:3]1([C@H:9]([N:11]2[C@@H:18]3[C@@H:14]([CH2:15][NH:16][CH2:17]3)[CH2:13][CH2:12]2)[CH3:10])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[OH-].[Na+]>C(O)=O>[CH3:1][N:16]1[CH2:17][C@@H:18]2[N:11]([C@@H:9]([C:3]3[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=3)[CH3:10])[CH2:12][CH2:13][C@@H:14]2[CH2:15]1

Komponenten

5

Edukt 3

HCID 712FormaldehydeHCID 14798Sodium HydroxideHCID 66757188(3aR,6aR)-1-((R)-1-Phenylethyl)octahydropyrrolo[3,4-b]pyrrole2×

Produkt 1

HCID 71269820(3aR,6aR)-5-methyl-1-[(1R)-1-phenylethyl]-2,3,3a,4,6,6a-hexahydropyrrolo[3,2-c]pyrroleAusbeute 70 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 284Formic AcidLösungsmittel

Reaktionsbedingungen

Temperatur
75 °C

Versuchsvorschrift

37% aqueous formaldehyde (1.6 L) was added to a solution of (3aR,6aR)-1-[(1R)-1-phenylethyl]-3,3a,4,5,6,6a-hexahydro-2H-pyrrolo[3,2-c]pyrrole (Intermediate 39, 108 g, 0.5 mol) in HCOOH (800 mL) at r.t., then the mixture was stirred at 70-80° C. for 2 h. The mixture was then cooled to 0° C. and basified with solid NaOH to pH-13. This mixture was then extracted with CH2Cl2 (2×2 L). The combined organic solutions were concentrated in vacuo. Purification by FCC, eluting with 2:1 to 1:10 hexanes/EtOAc, gave the title compound (80 g, 70%) as red oil; 1H NMR: (CDCl3) 1.36 (3H, d), 1.65 (1H, m), 1.85 (1H, m), 2.22 (3H, m), 2.32 (3H, s), 2.54 (1H, m), 2.68 (2H, m), 2.83 (1H, m), 3.10 (1H, m), 3.40 (1H, m), 7.21-7.33 (5H, m).

Aufarbeitung

  1. extractionThis mixture was then extracted with CH2Cl2 (2×2 L)
  2. concentrationThe combined organic solutions were concentrated in vacuo
  3. customPurification by FCC
  4. washeluting with 2:1 to 1:10 hexanes/EtOAc

Quellen und Nachweise

ORD-Eintrag
ord-02ee47d398544b589364cffdb85eb719
Quelldatensatz
uspto-grants-2015_02
Patentnummer
US08946235B2

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