Diethylamine → HCID 178453944, compound

HRID 861377Notes

Reaction equation

HRID 861377 reaction equation
[C:1]([O:5][C:6]([NH:8][C@H:9]1[CH2:14][CH2:13][C@H:12](NCC(OCC=C)=O)[CH2:11][CH2:10]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH2:23]([NH:25]CC)C>[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1COCC1>[C:1]([O:5][C:6]([NH:8][C@H:9]1[CH2:10][CH2:11][C@H:12]([CH2:23][NH2:25])[CH2:13][CH2:14]1)=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

5

Reactant 2

HCID 8021DiethylamineHCID 178459610HCID 178459610, compound

Product 1

HCID 178453944HCID 178453944, compoundYield 67.9%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To an Ar filled flask containing 5 g (4.33 mmol) of tetrakis(triphenylphosphine) palladium (Aldrich) and 15.92 g (50.96 mmol) of trans-4-t-butoxycarbonylaminocyclohexyl-(allyloxycarbonyl)methylamine was added 220 mL of dry THF. After the solids had dissolved, the solution was stirred for 5 min. and 50 mL (483 mmol) of diethylamine (Aldrich) was added in one portion. The solution was stirred at ambient temperature overnight. The solvents were removed by rotovap, and the residue partitioned between ice-cold 0.5M aq HCl and ethyl acetate. The organic layer was extracted with cold 0.5M aq HCl, and the combined aqueous layers washed with ethyl acetate, basified with aq NaOH and extracted with 3 x ethyl acetate. The combined organic layers were washed with water, brine, dried over Na2SO4 and solvents removed to give an oil that was chromatographed on 250 g of fine SiO2 using 90:10:1 chloroform-methanol-ammonium hydroxide to give 7.9 g (56%) of the title compound as a colorless semi-solid: NMR (CDCl3) d 0.5-1.5 (m, 4H), 1.8-1.3 (m, 1H), 1.44 (s, 9H), 1.81 (dm, J=10.3, 2H), 2.03 (din, J=10.3, 2H), 2.53 (d, J=6.6, 2H), 3.37 (br s, 1H), 4.44 (br s, 1H).

Workup

  1. additionTo an Ar filled flask
  2. dissolutionAfter the solids had dissolved
  3. stirringThe solution was stirred at ambient temperature overnight
  4. customThe solvents were removed by rotovap
  5. customthe residue partitioned between ice-cold 0.5M aq HCl and ethyl acetate
  6. extractionThe organic layer was extracted with cold 0.5M aq HCl
  7. washthe combined aqueous layers washed with ethyl acetate
  8. extractionextracted with 3 x ethyl acetate
  9. washThe combined organic layers were washed with water, brine
  10. dry with materialdried over Na2SO4 and solvents
  11. customremoved
  12. customto give an oil that
  13. customwas chromatographed on 250 g of fine SiO2 using 90:10:1 chloroform-methanol-ammonium hydroxide

Sources & evidence

ORD record
ord-ca4c7edb5b2d4391af1f4725f37f039c
Source dataset
uspto-grants-1998_02
Patent number
US05714485

Reaction notes

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