Acetic Acid → Salvinorin A

HRID 12320

Reaktionsgleichung

Reaktionsgleichung von HRID 12320
[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17]([OH:19])[C:16](=[O:20])[C@H:15]2[C@@:6]1([CH3:28])[CH2:7][CH2:8][C@H:9]1[C@:14]2([CH3:21])[CH2:13][C@@H:12]([C:22]2[CH:26]=[CH:25][O:24][CH:23]=2)[O:11][C:10]1=[O:27])=[O:4].C1(P(C2C=CC=CC=2)C2C=CC=CN=2)C=CC=CC=1.[C:48](O)(=[O:50])[CH3:49].CC(OC(/N=N/C(OC(C)(C)C)=O)=O)(C)C>C1COCC1.ClCCl>[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17]([O:19][C:48](=[O:50])[CH3:49])[C:16](=[O:20])[C@H:15]2[C@@:6]1([CH3:28])[CH2:7][CH2:8][C@@H:9]1[C@:14]2([CH3:21])[CH2:13][C@@H:12]([C:22]2[CH:26]=[CH:25][O:24][CH:23]=2)[O:11][C:10]1=[O:27])=[O:4]

Komponenten

7

Edukt 4

HCID 176Acetic AcidHCID 6218932-PyridyldiphenylphosphineHCID 6034084Di-tert-butyl diazene-1,2-dicarboxylateHCID 11395172(2S,4aS,6aR,7R,9S,10aS,10bR)-9-(hydroxy)-2-(3-furanyl)dodecahydro-6a,10b-dimethyl-4,10-dioxo-2H-naphtho[2,1-c]pyran-7-carboxylic acid methyl ester

Produkt 1

HCID 128563Salvinorin AAusbeute 81,6 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6344DichloromethaneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

A mixture of 8a (0.20 g, 0.51 mmol), diphenyl-2-pyridylphosphine (0.20 g, 0.77 mmol) and acetic acid (0.12 mL, 2.05 mmol) was dissolved in anhydrous THF (15 mL) under an argon atmosphere. To this solution was added di-tert-butylazodicarboxylate (DBAD) (0.18 g, 0.77 mmol) in one portion and the mixture was stirred for 18 hours at 60° C. The solvent was under reduced pressure and the residue was dissolved in dichloromethane (25 mL). The CH2Cl2 portion was washed with 4 M HCl (2×25 mL) and saturated NaCl (25 mL), and dried (Na2SO4). Removal of the solvent under reduced pressure afforded a crude residue. Flash column chromatography (eluent: n-hexanes/EtOAc, 7:3) gave 0.18 g (80%) of 34 as a white crystalline solid, mp 215-216° C.; 1H NMR (CDCl3): δ 1.10 (3H, s); 1.28 (1H, dd, J=6.0, 14.1); 1.45 (1H, m); 1.46 (3H, s); 1.64 (2H, m); 1.80 (1H, dd, J=3.0, 9.9); 2.10 (1H, m); 2.13 (3H, s); 2.18 (1H, ddd, J=3.3, 3.3, 15.0); 2.34 (1H, ddd, J=3.3, 13.0, 15.6); 2.45 (1H, dd, J=5.1, 13.5); 2.54 (1H, s); 2.90 (1H, dd, J=3.6, 13.2); 3.71 (3H, s); 4.85 (1H, dd, J=3.2, 3.2); 5.54 (1H, dd, J=5.1, 11.7); 6.38 (1H, dd, J=1.4, 1.7); 7.40 (2H, m); 13C NMR (CDCl3): δ 15.4, 16.3, 18.3, 21.2, 31.1, 35.2, 38.8, 43.2, 43.6, 51.1, 51.5, 52.1, 61.9, 72.3, 76.6, 108.5, 125.7, 139.4, 143.9, 169.6, 171.4, 172.4, 204.6; anal. C 63.63%, H 6.59%, O 29.70%, calcd for C25H28N2O7S, C 63.88%, H 6.53%, O 29.60%.

Aufarbeitung

  1. washThe CH2Cl2 portion was washed with 4 M HCl (2×25 mL) and saturated NaCl (25 mL)
  2. dry with materialdried (Na2SO4)
  3. customRemoval of the solvent under reduced pressure
  4. customafforded a crude residue

Quellen und Nachweise

ORD-Eintrag
ord-f9598e26fdd74eaabb3e1d58e0618d41
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07728001B2

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