N-tert-butoxycarbonyl O-allyl L-seryl L-valyl L-valine methyl ester → O-allyl L-seryl L-valyl L-valine methyl ester

HRID 2370895Notes

Reaction equation

HRID 2370895 reaction equation
[CH3:1][O:2][C:3](=[O:32])[C@H:4]([CH:29]([CH3:31])[CH3:30])[NH:5][C:6](=[O:28])[C@H:7]([CH:25]([CH3:27])[CH3:26])[NH:8][C:9](=[O:24])[C@H:10]([CH2:19][O:20][CH2:21][CH:22]=[CH2:23])[NH:11]C(OC(C)(C)C)=O>C(O)=O>[CH3:1][O:2][C:3](=[O:32])[C@H:4]([CH:29]([CH3:31])[CH3:30])[NH:5][C:6](=[O:28])[C@H:7]([CH:25]([CH3:27])[CH3:26])[NH:8][C:9](=[O:24])[C@H:10]([CH2:19][O:20][CH2:21][CH:22]=[CH2:23])[NH2:11]

Participants

3

Reactant 1

HCID 86671348N-tert-butoxycarbonyl O-allyl L-seryl L-valyl L-valine methyl ester

Product 1

HCID 86671349O-allyl L-seryl L-valyl L-valine methyl esterYield 82%

Reagents, catalysts & solvents 1

HCID 284Formic AcidSolvent

Procedure

N-tert-butoxycarbonyl O-allyl L-seryl L-valyl L-valine methyl ester (8) (6.80 g, 14.9 mmol) was stirred in formic acid (70 mL) at room temperature for 9 hours and the formic acid evaporated. The residue was diluted with 110 mL water and the aqueous solution washed with Et2O (3×30 mL). The pH was adjusted to pH 9 by addition of solid K2CO3 and the resulting solution extracted with EtOAc (3×55 mL). The combined organic extracts were washed with saturated brine (30 mL) and dried with anhydrous MgSO4. The solvent was evaporated affording a white solid (4.35 g, 82%); δH (200 MHz; do-DMSO) 8.26 (1H, d, J 8, NH(Valx)), 8.03 (1H, d, J 9, NH(Valy)), 5.85 (1H, ddt, J 5, 10 and 17, CH═CH2)), 5.24 (1H, ddt, J 1, 3 and 17, CH═CHH), 5.12 (1H, ddt, J 1, 3 and 10, CH═CHH), 4.36 (1H, dd, J 6 and 9, CαH(Valy)), 4.12 (1H, dd, J 6 and 8, CαH(Valx)), 3.93 (2H, dt, J 1 and 5, CH2CH═CH2), 3.61 (3H, s, OCH3), 3.49 (2H, d, J 5, CH2,), 3.43-3.39 (1H, m, CαH(Ser(All))), 2.38 (2H, br s, NH2), 2.12-1.86 (2H, m, CH(CH3)2), 0.91-0.78 (12H, m, CH3)

Workup

  1. customthe formic acid evaporated
  2. additionThe residue was diluted with 110 mL water
  3. washthe aqueous solution washed with Et2O (3×30 mL)
  4. additionThe pH was adjusted to pH 9 by addition of solid K2CO3
  5. extractionthe resulting solution extracted with EtOAc (3×55 mL)
  6. washThe combined organic extracts were washed with saturated brine (30 mL)
  7. dry with materialdried with anhydrous MgSO4
  8. customThe solvent was evaporated

Sources & evidence

ORD record
ord-d3d177dc842b46dd9de69c6f9196a081
Source dataset
uspto-grants-2014_04
Patent number
US08710008B2

Reaction notes

Loading…