HCID 86622990, compound → HCID 86622991, compound

HRID 2190113Notes

Reaction equation

HRID 2190113 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH2:9][C@H:10]([NH:24]C(OC(C)(C)C)=O)[C:11]([O:13][C@H:14]([CH3:23])[C@H:15]([O:17][C:18](=[O:22])[CH:19]([CH3:21])[CH3:20])[CH3:16])=[O:12])[CH:5]=[CH:6][C:7]=1[OH:8]>Cl.O1CCOCC1>[NH2:24][C@@H:10]([CH2:9][C:4]1[CH:5]=[CH:6][C:7]([OH:8])=[C:2]([OH:1])[CH:3]=1)[C:11]([O:13][C@H:14]([CH3:23])[C@H:15]([O:17][C:18](=[O:22])[CH:19]([CH3:21])[CH3:20])[CH3:16])=[O:12]

Participants

4

Reactant 1

HCID 86622990HCID 86622990, compound

Product 1

HCID 86622991HCID 86622991, compoundYield 80.5%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 312751,4-DioxaneSolvent2×

Procedure

(1R,2R)-1-Methyl-2-(2-methylpropanoyloxy)propyl (2S)-3-(3,4-dihydroxyphenyl)-2-[(tert-butoxy)carbonylamino]propanoate (18) (6.7 g, 15 mmol) was dissolved in 20 ml of 4M HCl in 1,4-dioxane. The resulting mixture was stirred at room temperature for 60 min. dioxane and then evaporated completely under reduced pressure. The residue was dissolved in acetonitrile (20 mL). The solution was stirred at room temperature. The product was crystallized as hydrogen chloride salt, which was collected by filtration and dried under vacuum to give the title compound (9) (4.1 g, 75% yield). m.p.: 164.7-166.2° C. 1H NMR (400 MHz, CD3OD): δ 1.15 (d, 3H, J=6.8 Hz), 1.16 (d, 3H, J=6.8 Hz), 1.18 (d, 3H, J=6.8 Hz), 1.19 (d, 3H, J=6.4 Hz), 2.55 (m, 1H, J=6.8 Hz), 3.03 (dd, 1H, J=12.4, 6.8 Hz), 3.07 (dd, 1H, J=14.4, 6.8 Hz), 4.20 (t, 1H, J=6.8 Hz), 4.96 (m, 1H), 5.05 (m, 1H), 6.57 (dd, 1H, J=2, 8 Hz), 6.67 (d, 1H, J=2 Hz), 6.74 (d, 1H, J=8 Hz). MS (ESI) m/z 340.1 (M+H)+ and 338.1 (M−H), de>98% (by HPLC on Chiralpak column).

Workup

  1. customevaporated completely under reduced pressure
  2. dissolutionThe residue was dissolved in acetonitrile (20 mL)
  3. customThe product was crystallized as hydrogen chloride salt, which
  4. filtrationwas collected by filtration
  5. customdried under vacuum

Sources & evidence

ORD record
ord-7d9cfe182fe248d681c592ee71914677
Source dataset
uspto-grants-2012_12
Patent number
US08324272B2

Reaction notes

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