Bis(4-nitrophenyl) carbonate → tert-butyl (2S,3S)-3-methyl-2-{3-[(2-methyl-1,3-thiazol-4-yl)methyl]-2-oxo-1-imidazolidinyl}pentanoate

HRID 1174144Notes

Reaction equation

HRID 1174144 reaction equation
[NH2:1][CH2:2][CH2:3][NH:4][C@@H:5]([C@@H:13]([CH3:16])[CH2:14][CH3:15])[C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7].[CH3:17][C:18]1[S:19][CH:20]=[C:21]([CH:23]=O)[N:22]=1.[BH4-].[Na+].[C:27](=O)(OC1C=CC([N+]([O-])=O)=CC=1)[O:28]C1C=CC([N+]([O-])=O)=CC=1>C1C=CC=CC=1.CO.C1(C)C=CC=CC=1>[CH3:16][C@@H:13]([CH2:14][CH3:15])[C@H:5]([N:4]1[CH2:3][CH2:2][N:1]([CH2:23][C:21]2[N:22]=[C:18]([CH3:17])[S:19][CH:20]=2)[C:27]1=[O:28])[C:6]([O:8][C:9]([CH3:10])([CH3:11])[CH3:12])=[O:7]

Participants

8

Reactant 4

HCID 78756Bis(4-nitrophenyl) carbonateHCID 27631912-Methyl-1,3-thiazole-4-carbaldehydeHCID 4311764Sodium borohydrideHCID 86598803tert-butyl(2S,3S)-2-[(2-aminoethyl)amino]-3-methylpentanoate

Product 1

HCID 67410059tert-butyl (2S,3S)-3-methyl-2-{3-[(2-methyl-1,3-thiazol-4-yl)methyl]-2-oxo-1-imidazolidinyl}pentanoateYield 69%

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 887MethanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
50 °C

Procedure

A solution containing the product from Example 3G (1.81 g, 7.9 mmol) in a mixture of benzene (8 mL) and methanol (8 mL) was treated with the product from Example 11B (1.0 g, 7.9 mmol), stirred at 50° C. for 1 hour, cooled to 25° C. and treated with sodium borohydride (0.60 g, 15.7 mmol), stirred at 25° C. for 1 hour, quenched with sodium bicarbonate solution and partitioned between ethyl acetate and water. The organic phase was washed with brine, dried over Na2SO4, filtered and concentrated. A solution of the residue (7.9 mmol) in toluene (16 mL) was treated with bis(4-nitrophenyl) carbonate (2.87 g, 9.4 mmol), stirred at reflux for 16 hours, cooled to 25° C. and partitioned between ethyl acetate and 10% K2CO3. The organic phase was washed with brine, dried over Na2SO4, filtered and concentrated. The residue was chromatographed on silica gel eluting with 1% methanol in chloroform to give the title compound (2.0 g, 69% yield).

Workup

  1. temperaturecooled to 25° C.
  2. stirringstirred at 25° C. for 1 hour
  3. customquenched with sodium bicarbonate solution
  4. custompartitioned between ethyl acetate and water
  5. washThe organic phase was washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. stirringstirred
  10. temperatureat reflux for 16 hours
  11. temperaturecooled to 25° C.
  12. custompartitioned between ethyl acetate and 10% K2CO3
  13. washThe organic phase was washed with brine
  14. dry with materialdried over Na2SO4
  15. filtrationfiltered
  16. concentrationconcentrated
  17. customThe residue was chromatographed on silica gel eluting with 1% methanol in chloroform

Sources & evidence

ORD record
ord-c14e16154a07459d8e9d2b3a47990f8a
Source dataset
uspto-grants-2010_11
Patent number
US07834043B2

Reaction notes

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