Hydrochloric Acid → (R)-2-Methyl-2-(2-trimethylsilanyl-ethoxymethyl)-but-3-enoic acid

HRID 2285347Notes

Reaction equation

HRID 2285347 reaction equation
C([C@@H]1COC(=O)N1[C:10](=[O:23])[C@@:11]([CH3:22])([CH2:14][O:15][CH2:16][CH2:17][Si:18]([CH3:21])([CH3:20])[CH3:19])[CH:12]=[CH2:13])(C)C.OO.O.[OH-].[Li+].S(S([O-])=O)([O-])(=O)=[O:30].[Na+].[Na+].Cl>O1CCCC1.O>[CH3:22][C@:11]([CH2:14][O:15][CH2:16][CH2:17][Si:18]([CH3:19])([CH3:20])[CH3:21])([CH:12]=[CH2:13])[C:10]([OH:23])=[O:30]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 168937Lithium hydroxide, monohydrateHCID 656671Sodium PyrosulfiteHCID 86709642(R)-4-Isopropyl-3-[(R)-2-methyl-2-(2-trimethylsilanyl-ethoxymethyl)-but-3-enoyl]-oxazolidin-2-one

Product 1

HCID 86709643(R)-2-Methyl-2-(2-trimethylsilanyl-ethoxymethyl)-but-3-enoic acidYield 88%

Reagents, catalysts & solvents 1

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

Conditions

Temperature
0 °C

Procedure

A cooled (0° C.) solution of (R)-4-isopropyl-3-[(R)-2-methyl-2-(2-trimethylsilanyl-ethoxymethyl)-but-3-enoyl]-oxazolidin-2-one (543.3 mg, 1.591 mmol) in tetrahydrofuran/water (15 mL, 2:1) was subsequently treated with hydrogen peroxide (30%, 820 μL, 7.955 mmol) and lithium hydroxide monohydrate (133.5 mg, 3.181 mmol). After stirring at 0° C. for 2 h, the reaction was quenched with solid sodium metabisulfite (3 g, 16 mmol). After stirring at room temperature for 30 min, the mixture was acidified with hydrochloric acid (1 M) to pH 2, the aqueous layer was extracted with dichloromethane (2×). The organics were combined, filtered through a phase separator and the volatiles were removed in vacuo. The residue was purified by silica gel chromatography using a 50 g Isolute cartridge eluted with a continuous gradient of iso-hexanes/ethyl acetate 1:0 to 4:1 to afford the title compound (322.3 mg, 88%) as a colourless oil. 1H NMR (300 MHz, CDCl3) δ 0.03 (s, 9H), 0.98 (app t, J=8.5 Hz, 2H), 1.34 (s, 3H), 3.46 (d, J=8.9 Hz, 1H), 3.57-3.67 (m, 3H), 5.19-5.29 (m, 2H), 6.00 (dd, J=17.4, 10.7 Hz, 1H), 10.80 (br s, 1H).

Workup

  1. stirringAfter stirring at room temperature for 30 min
  2. extractionthe aqueous layer was extracted with dichloromethane (2×)
  3. filtrationfiltered through a phase separator
  4. customthe volatiles were removed in vacuo
  5. customThe residue was purified by silica gel chromatography
  6. washeluted with a continuous gradient of iso-hexanes/ethyl acetate 1:0 to 4:1

Sources & evidence

ORD record
ord-dd8f1c8e05a44ecc9d741e2009b8cd10
Source dataset
uspto-grants-2015_09
Patent number
US09145441B2

Reaction notes

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