Sodium Sulfite → ethyl 5-((1R,2S)-1,2-dihydroxypropyl)-4-methylisoxazole-3-carboxylate

HRID 1478206Notes

Reaction equation

HRID 1478206 reaction equation
[CH3:1][C:2]1[C:3]([C:10]([O:12][CH2:13][CH3:14])=[O:11])=[N:4][O:5][C:6]=1/C=C/C.CC[C@@H]1[C@@H]2C[C@H]([C@@H](OC3C4C(=CC=CC=4)C(O[C@@H](C4C=CN=C5C=4C=C(OC)C=C5)[C@@H]4N5C[C@H](CC)[C@@H](CC5)C4)=NN=3)C3C=CN=C4C=3C=C([O:36]C)C=C4)N(CC2)C1.CS(N)(=O)=O.S([O-])([O-])=O.[Na+].[Na+].[C:84]([OH:88])([CH3:87])([CH3:86])C.O>C(O)(C)(C)C.[Os](=O)(=O)(=O)=O>[OH:36][C@@H:86]([C:6]1[O:5][N:4]=[C:3]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:2]=1[CH3:1])[C@@H:84]([OH:88])[CH3:87]

Participants

8

Reactant 5

HCID 24437Sodium SulfiteHCID 72879MethanesulfonamideHCID 112172021,4-Bis(dihydroquinidine)phthalazineHCID 714019492-Methylpropan-2-ol--water (1/1)2×HCID 125490638(E)-Ethyl 4-methyl-5-(prop-1-en-1-yl)isoxazole-3-carboxylate

Product 1

HCID 118511095ethyl 5-((1R,2S)-1,2-dihydroxypropyl)-4-methylisoxazole-3-carboxylate

Reagents, catalysts & solvents 2

HCID 30318Osmium TetroxideCatalystHCID 6386tert-ButanolSolvent

Procedure

(E)-Ethyl 4-methyl-5-(prop-1-en-1-yl)isoxazole-3-carboxylate (500 mg, 2.56 mmol) in tert-BuOH-water (1 mL) was added portionwise to a mixture of AD-mix-beta (3.59 g, 7.63 mmol), methane sulfonamide (731 mg, 7.68 mmol), modified AD-mix-β (DHQD)2PHAL (80 mg, 0.102 mmol) and osmium tetroxide (0.836 mL of a 2.5 wt % solution in tert-BuOH, 0.067 mmol) in tert-BuOH-water (1:1, 19 mL) and the resulting reaction mixture was stirred at room temperature for 1.5 hr. Sodium sulfite (3.9 g) was added in one portion and the reaction was left to stir for 30 mins. The phases were separated and the EtOAc phase was dried over Na2SO4 and concentrated under reduced pressure. The crude material was adsorbed onto silica and purification by chromatography eluting with 65-75% EtOAc in iso-hexane afforded the title compound (96% ee);

Workup

  1. waitthe reaction was left
  2. stirringto stir for 30 mins
  3. customThe phases were separated
  4. dry with materialthe EtOAc phase was dried over Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customThe crude material was adsorbed onto silica and purification by chromatography
  7. washeluting with 65-75% EtOAc in iso-hexane

Sources & evidence

ORD record
ord-866df877ce7e49eb8e0b95f70782adce
Source dataset
uspto-grants-2016_08
Patent number
US09403810B2

Reaction notes

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