m-Chloroperbenzoic acid → HCID 58630860, compound

HRID 1823333Notes

Reaction equation

HRID 1823333 reaction equation
[CH3:1][O:2][C@H:3]([CH3:24])[C@H:4]([NH:20]CC#N)[CH2:5][S:6]([CH2:9][C:10]1[CH:11]=[N:12][C:13]2[C:18]([CH:19]=1)=[CH:17][CH:16]=[CH:15][CH:14]=2)(=[O:8])=[O:7].O.C1(C)C=CC(S(O)(=O)=[O:33])=CC=1.ClC1C=C(C=CC=1)C(OO)=O>>[CH3:1][O:2][C@H:3]([CH3:24])[C@H:4]([NH:20][OH:33])[CH2:5][S:6]([CH2:9][C:10]1[CH:11]=[N:12][C:13]2[C:18]([CH:19]=1)=[CH:17][CH:16]=[CH:15][CH:14]=2)(=[O:8])=[O:7]

Participants

4

Reactant 3

HCID 70297m-Chloroperbenzoic acidHCID 521998p-Toluenesulfonic acid monohydrateHCID 58630868HCID 58630868, compound

Product 1

HCID 58630860HCID 58630860, compoundYield 357.7%

Conditions

Temperature
60 °C

Procedure

An ice-cold stirred solution of (2S,3R)-3-methoxy-2-(N-cyanomethylamino)-1-(3-quinolylmethanesulfonyl)butane (590 mg) in MDC (20 ml) was treated with 4-toluenesulphonic acid monohydrate (50 mg) and 70% 3-chloroperoxybenzoic acid (281 mg). After 45 min the reaction was quenched with 10% sodium thiosulphate (5 ml) followed by saturated sodium hydrogen carbonate (5 ml) solution. After 5 min the organic layer was collected and the aqueous re-extracted with MDC (10 ml). The combined MDC phases were dried (MgSO4) and evaporated. The residue was redissolved in methanol (10 ml) treated with 4-toluenesulphonic acid monohydrate and hydroxylamine hydrochloride (2.36 g) and heated at 60° C. for 1.5 h. The cooled solution was evaporated, then dissolved in water (5 ml) and saturated sodium hydrogen carbonate solution (5 ml). After extraction with MDC (2×5 ml), the combined extracts were dried (MgSO4) and evaporated. The residue was flash chromatographed (silica gel, step gradient: 80–100% ethyl acetate in hexane) to give the subtitle compound (305 mg). MS (APCI+ve ion) 325(MH+); 1H NMR δ(CDCl3): 8.91 (1H, m), 8.32 (1H, d, J=2 Hz), 8.14 (1H, d, J=8 Hz), 7.85 (1H, d, J=8 Hz), 7.76 (1H, t, J=8 Hz), 7.6 (1H, t, J=8 Hz), 4.83 (1H, broad), 4.58 (2H, m), 3.0–3.7 (4H, m), 3.38 (3H, s), 0.92 (3H, d, J=6.3 Hz).

Workup

  1. customAfter 45 min the reaction was quenched with 10% sodium thiosulphate (5 ml)
  2. customAfter 5 min the organic layer was collected
  3. extractionthe aqueous re-extracted with MDC (10 ml)
  4. dry with materialThe combined MDC phases were dried (MgSO4)
  5. customevaporated
  6. dissolutionThe residue was redissolved in methanol (10 ml)
  7. additiontreated with 4-toluenesulphonic acid monohydrate and hydroxylamine hydrochloride (2.36 g)
  8. customThe cooled solution was evaporated
  9. dissolutiondissolved in water (5 ml)
  10. extractionAfter extraction with MDC (2×5 ml)
  11. dry with materialthe combined extracts were dried (MgSO4)
  12. customevaporated
  13. customchromatographed (silica gel, step gradient: 80–100% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-d2ac04c1f9b348ef88a56c9e25ba5272
Source dataset
uspto-grants-2006_05
Patent number
US07038055B2

Reaction notes

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