Vanillin → N-benzyloxycarbony-D-valine isopropylamide

HRID 1382049Notes

Reaction equation

HRID 1382049 reaction equation
[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([C:16]([OH:18])=O)[CH:13]([CH3:15])[CH3:14])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:19]([NH2:22])([CH3:21])[CH3:20].O=CC1C=CC(O)=C(OC)C=1>C(OCC)(=O)C.CCCCCC>[CH:19]([NH:22][C:16](=[O:18])[C@@H:12]([CH:13]([CH3:14])[CH3:15])[NH:11][C:9]([O:8][CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)=[O:10])([CH3:21])[CH3:20]

Participants

5

Reactant 3

HCID 1183VanillinHCID 6363IsopropylamineHCID 712434N-alpha-Benzyloxycarbonyl-D-valine

Product 1

HCID 14723623N-benzyloxycarbony-D-valine isopropylamide

Reagents, catalysts & solvents 1

HCID 21226206Ethyl acetate hexaneSolvent

Procedure

Reaction of N-benzyloxycarbonyl-D-valine with isopropylamine by the method of Example 20, Part A afforded a quantitative yield of N-benzyloxycarbonyl-D-valine isopropylamide of Rf 0.61 (TLC, ethyl acetate/hexane, 1:1, vanillin spray). Hydrogenolysis over Pd/C by the method of Example 20, Part B gave D-valine isopropylamide in 71% yield, Rf 0.50. Coupling with beta-benzyl N-Cbz-L-asparate provided the diblocked dipeptide amide (procedure of Example 20, Part C), Rf 0.40 (TLC, ethyl acetate/hexane, 1, vanillin spray), in 62% yield as an off-white solid. This was converted to the desired title compound by the procedure of Example 20, Part D, in 90.6% yield, M.P. 226°-227° C. (decomp.), Rf 0.44. Sweetness, 1-2 x sucrose.

Sources & evidence

ORD record
ord-c7b948592530464b9fc0f53a7f531629
Source dataset
uspto-grants-1989_02
Patent number
US04804782

Reaction notes

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