Hydrochloric Acid → (E)-(R)-2-Cyclopropylmethyl-pent-3-enoic acid

HRID 2285353Notes

Reaction equation

HRID 2285353 reaction equation
C([C@H]1COC(=O)N1[C:14](=[O:23])[C@H:15]([CH2:19][CH:20]1[CH2:22][CH2:21]1)/[CH:16]=[CH:17]/[CH3:18])C1C=CC=CC=1.OO.O.[OH-].[Li+].S(S([O-])=O)([O-])(=O)=[O:30].[Na+].[Na+].Cl>O1CCCC1.O>[CH:20]1([CH2:19][C@H:15](/[CH:16]=[CH:17]/[CH3:18])[C:14]([OH:23])=[O:30])[CH2:21][CH2:22]1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 168937Lithium hydroxide, monohydrateHCID 656671Sodium PyrosulfiteHCID 86709649(S)-4-benzyl-3-((E)-(R)-2-cyclopropylmethyl-pent-3-enoyl)-oxazolidin-2-one

Product 1

HCID 86709648(E)-(R)-2-Cyclopropylmethyl-pent-3-enoic acidYield 78%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of (S)-4-benzyl-3-((E)-(R)-2-cyclopropylmethyl-pent-3-enoyl)-oxazolidin-2-one (3.50 g, 10.92 mmol) in tetrahydrofuran (75 mL) was cooled to 0° C. before addition of a 30% aqueous solution of hydrogen peroxide (5.8 mL, 56 mmol) and a solution of lithium hydroxide monohydrate (950 mg, 22.6 mmol) in water (37 mL). The reaction was stirred at 0° C. for 2.5 h. The reaction mixture was treated with an aqueous solution of sodium metabisulphite and stirred for 10 minutes before acidifying to pH 1 with hydrochloric acid (2 M). The mixture was extracted with ethyl acetate (3×50 mL). The extract was dried over anhydrous sodium sulfate, filtered and evaporated to give a colourless oil. The oil was purified by silica gel chromatography using iso-hexanes/ethyl acetate 7:3 to yield the title compound (1.32 g, 78%) as a colourless oil and as a mixture of 2.5:1 E/Z isomers. 1H NMR (300 MHz, CDCl3) δ 0.02-0.15 (m, 1.96H), 0.39-0.52 (m, 1.96H), 0.65-0.81 (m, 0.98H), 1.47-1.63 (m, 1.96H), 1.71 (d, J=6.7 Hz, 2.94H), 3.06-3.17 (m, 0.98H), 3.45-3.56 (m, 0.28H), 5.40-5.56 (m, 0.98H), 5.57-5.72 (m, 0.98H), 10.5-12.0 (bs, LCMS (m/z) 153.1 [M−H], Tr=1.91 min.

Workup

  1. stirringstirred for 10 minutes
  2. extractionThe mixture was extracted with ethyl acetate (3×50 mL)
  3. dry with materialThe extract was dried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customto give a colourless oil
  7. customThe oil was purified by silica gel chromatography

Sources & evidence

ORD record
ord-34daaafbb5794762bb033b6af110c42d
Source dataset
uspto-grants-2015_09
Patent number
US09145441B2

Reaction notes

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