Bis(4-nitrophenyl) carbonate → HCID 67406680, compound

HRID 1174275Notes

Reaction equation

HRID 1174275 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].[CH:17]([C:20]1[S:21][CH:22]=[C:23]([CH:25]=O)[N:24]=1)([CH3:19])[CH3:18].[BH4-].[Na+].[N+](C1C=C[C:35]([O:38]C(=O)OC2C=CC([N+]([O-])=O)=CC=2)=CC=1)([O-])=O>C1C=CC=CC=1.CO>[CH:17]([C:20]1[S:21][CH:22]=[C:23]([CH2:25][N:1]2[CH2:2][CH2:3][N:4]([C@@H:5]([C@@H:13]([CH3:16])[CH2:14][CH3:15])[C:6]([O:8][C:9]([CH3:10])([CH3:11])[CH3:12])=[O:7])[C:35]2=[O:38])[N:24]=1)([CH3:18])[CH3:19]

Participants

7

Reactant 4

HCID 78756Bis(4-nitrophenyl) carbonateHCID 27631922-Isopropylthiazole-4-carbaldehydeHCID 4311764Sodium borohydrideHCID 86598803tert-butyl(2S,3S)-2-[(2-aminoethyl)amino]-3-methylpentanoate

Product 1

HCID 67406680HCID 67406680, compoundYield 75%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 887MethanolSolvent

Conditions

Temperature
50 °C

Procedure

A solution containing the product from Example 3G (1.304 g, 5.66 mmol) in a mixture of benzene (15 mL) and methanol (15 mL) was treated with the product from Example 97A (1.05 g, 6.79 mmol), was heated at 50° C. for 3 hours, cooled to 0° C., treated with sodium borohydride (0.428 g, 11.32 mmol), stirred at 25° C. for 16 hours, quenched with sodium bicarbonate solution, and partitioned between ethyl acetate and water. The organic phase was washed with brine and dried over MgSO4, filtered and concentrated. A solution of the concentrate (5.66 mmol) in toluene (30 mL) was treated with bis(4-nitrophenyl)carbonate (2.066 g, 6.79 mmol), heated at 100° C. for 16 hours, cooled and partitioned between ethyl acetate and saturated NaHCO3. The organic phase was washed with brine and dried over MgSO4, filtered and concentrated. The residue was chromatographed on silica gel eluting with 0-25% ethyl acetate in dichloromethane to give the title compound (1.68 g, 75% yield).

Workup

  1. temperaturecooled to 0° C.
  2. customquenched with sodium bicarbonate solution
  3. custompartitioned between ethyl acetate and water
  4. washThe organic phase was washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. concentrationA solution of the concentrate (5.66 mmol) in toluene (30 mL)
  9. temperatureheated at 100° C. for 16 hours
  10. temperaturecooled
  11. custompartitioned between ethyl acetate and saturated NaHCO3
  12. washThe organic phase was washed with brine
  13. dry with materialdried over MgSO4
  14. filtrationfiltered
  15. concentrationconcentrated
  16. customThe residue was chromatographed on silica gel eluting with 0-25% ethyl acetate in dichloromethane

Sources & evidence

ORD record
ord-fe952add77c44a358101992ef4273d6d
Source dataset
uspto-grants-2010_11
Patent number
US07834043B2

Reaction notes

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