Hydrogen Peroxide → (R)-2-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-but-3-enoic acid

HRID 2285360Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2285360
[C:1]([Si:5]([CH3:26])([CH3:25])[O:6][C@@H:7]([C@@H:9]([CH:23]=[CH2:24])[C:10](N1[C@H](C(C)C)C(C)(C)OC1=O)=[O:11])[CH3:8])([CH3:4])([CH3:3])[CH3:2].[OH:27]O.O.[OH-].[Li+]>O1CCCC1.O>[C:1]([Si:5]([CH3:26])([CH3:25])[O:6][C@@H:7]([C@@H:9]([CH:23]=[CH2:24])[C:10]([OH:11])=[O:27])[CH3:8])([CH3:2])([CH3:3])[CH3:4]

Komponenten

5

Edukt 3

HCID 784Hydrogen PeroxideHCID 168937Lithium hydroxide, monohydrateHCID 86709655(R)-3-{(R)-2-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-but-3-enoyl}-4-isopropyl-5,5-dimethyl-oxazolidin-2-one

Produkt 1

HCID 86709657(R)-2-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-but-3-enoic acidAusbeute 79 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 21881883Oxolane--water (1/1)Lösungsmittel

Versuchsvorschrift

A cooled (0° C.) solution of (R)-3-{(R)-2-[(R)-1-(tert-butyl-dimethyl-silanyloxy)-ethyl]-but-3-enoyl}-4-isopropyl-5,5-dimethyl-oxazolidin-2-one (400 mg, 1.04 mmol) in tetrahydrofuran/water (15 mL, 2:1) was subsequently treated with hydrogen peroxide (30% aqueous, 537 μL, 5.21 mmol) and lithium hydroxide monohydrate (87 mg, 2.09 mmol). The mixture was allowed to warm up to room temperature overnight. The reaction was quenched with sodium metabisulfite until Kl/starch paper negative. After stirring for 2 h at room temperature the volatiles were removed in vacuo. The mixture was then diluted with water and the pH was adjusted with potassium carbonate. The aqueous layer was washed with dichloromethane (2×20 mL) and acidified with hydrochloric acid (pH˜1) then extracted with ethyl acetate (3×30 mL). All ethyl acetate layers were combined and the volatiles were removed in vacuo to afford the title compound (200 mg, 79%) as a clear oil. 1H NMR (300 MHz, CDCl3) δ 0.09 (s, 3H), 0.11 (s, 3H), 0.89 (s, 9H), 1.22 (d, J=6.0 Hz, 3H), 3.07 (t, J=8.7 Hz, 4.11 (pentet, J=6.5 Hz, 1H), 5.20-5.35 (m, 2H), 5.70-5.90 (m, 1H).

Aufarbeitung

  1. customThe reaction was quenched with sodium metabisulfite until Kl/starch paper negative
  2. customwere removed in vacuo
  3. additionThe mixture was then diluted with water
  4. washThe aqueous layer was washed with dichloromethane (2×20 mL)
  5. extractionthen extracted with ethyl acetate (3×30 mL)
  6. customthe volatiles were removed in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-b0010bfd255f4c11962315fd5043429e
Quelldatensatz
uspto-grants-2015_09
Patentnummer
US09145441B2

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