Potassium Carbonate → 2,2-Dimethyl-propionic acid (2S,3S,4R,5R)-3,5-dimethoxy-2,4-dimethyl-hept-6-ynyl ester

HRID 1427757

Reaktionsgleichung

Reaktionsgleichung von HRID 1427757
[CH3:1][O:2][C@H:3]([C@@H:14]([CH3:20])[C@@H:15]([O:18][CH3:19])[CH:16]=O)[C@@H:4]([CH3:13])[CH2:5][O:6][C:7](=[O:12])[C:8]([CH3:11])([CH3:10])[CH3:9].[N+](=[C:23](P(=O)(OCC)OCC)C(=O)C)=[N-].C(=O)([O-])[O-].[K+].[K+]>CO>[CH3:1][O:2][C@H:3]([C@@H:14]([CH3:20])[C@@H:15]([O:18][CH3:19])[C:16]#[CH:23])[C@@H:4]([CH3:13])[CH2:5][O:6][C:7](=[O:12])[C:8]([CH3:9])([CH3:10])[CH3:11]

Komponenten

5

Edukt 3

HCID 11430Potassium CarbonateHCID 866758512,2-Dimethyl-propionic acid (2S,3S,4R,5R)-3,5-dimethoxy-2,4-dimethyl-6-oxo-hexyl esterHCID 136104435(1Z)-1-diazo-1-diethoxyphosphorylpropan-2-one

Produkt 1

HCID 866758562,2-Dimethyl-propionic acid (2S,3S,4R,5R)-3,5-dimethoxy-2,4-dimethyl-hept-6-ynyl ester

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To 2,2-Dimethyl-propionic acid (2S,3S,4R,5R)-3,5-dimethoxy-2,4-dimethyl-6-oxo-hexyl ester (2.0 g, 6.94 mmol) in anhydrous methanol (100 ml) at 0° C. and under an atmosphere of nitrogen was added diethyl 1-diazo-2-oxopropylphosphonate (1.6 ml, 10.4 mmol) and potassium carbonate (1.44 g, 10.4 mmol). The reaction was stirred at 0° C. for 1 hour and then room temperature for 2 hours, after which it was quenched with saturated ammonium chloride and extracted with diethyl ether (3×). The combined organic layers were dried over magnesium sulphate, filtered and concentrated in vacuo. The product was purified by flash chromatography (SiO2, iHex/EtOAc, 15:1) to afford 1.67 g (85%) as a clear oil. 1H NMR (300 MHz, CDCl3) δ 4.22 (dd, J=10.7 Hz, 3.6 Hz, 1H), 4.07 (dd, J=10.7 Hz, 5.8 Hz, 1H), 3.87 (dd, J=9.6 Hz, 2.0 Hz, 1H), 3.46 (s, 3H), 3.44 (m, 1H), 3.40 (s, 3H), 2.48 (d, J=2.0 Hz, 1H), 1.97 (m, 2H), 1.23 (s, 9H), 1.00 (d, J=6.9 Hz, 3H), 0.92 (d, J=6.9 Hz, 3H).

Aufarbeitung

  1. waitroom temperature for 2 hours
  2. customafter which it was quenched with saturated ammonium chloride
  3. extractionextracted with diethyl ether (3×)
  4. dry with materialThe combined organic layers were dried over magnesium sulphate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe product was purified by flash chromatography (SiO2, iHex/EtOAc, 15:1)
  8. customto afford 1.67 g (85%) as a clear oil

Quellen und Nachweise

ORD-Eintrag
ord-f72f7471f61647218b6427a8b287f4f3
Quelldatensatz
uspto-grants-2015_01
Patentnummer
US08933015B2

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