Reaktion #1154240

ord-b9b01da9b23a47ad8e081d38b9ec2dc2

Reaktionsgleichung

Nc1ccn([C@H]2C[C@H](OP(=O)(O)OC[C@H]3O[C@@H](n4cnc5c(N)ncnc54)[C@H](O)[C@@H]3O)[C@@H](COP(=O)(O)O)O2)c(=O)n1
pdCpA
C=CCCC(=O)OC(=O)CCC=C
ester
C=CCCC(=O)OC(=O)CCC=C
4-pentenoic anhydride
[Li+].[OH-]
LiOH
C=CCC(NC(=O)OCc1ccccc1)C(=O)N[C@H](C(=O)OCc1ccccc1)C(C)C
N-(N-benzyloxycarbonyl-2-amino-4-Pentenoyl)-L-valine benzyl ester
C=CCC(NC(=O)OCc1ccccc1)C(=O)N[C@H](C(=O)OCc1ccccc1)C(C)C
cyanomethyl ester
→
CC(C)[C@H](N)C(=O)OCc1ccccc1
N-(4-pentenoyl)valyl-pdCpA
Ausbeute 94.0%
CC(C)[C@H](N)C(=O)OCc1ccccc1
valine benzyl ester
Ausbeute 94.0%

Edukte

Nc1ccn([C@H]2C[C@H](OP(=O)(O)OC[C@H]3O[C@@H](n4cnc5c(N)ncnc54)[C@H](O)[C@@H]3O)[C@@H](COP(=O)(O)O)O2)c(=O)n1
pdCpA
C=CCCC(=O)OC(=O)CCC=C
ester
C=CCCC(=O)OC(=O)CCC=C
4-pentenoic anhydride
[Li+].[OH-]
LiOH
—
Nucleic Acids
C=CCC(NC(=O)OCc1ccccc1)C(=O)N[C@H](C(=O)OCc1ccccc1)C(C)C
N-(N-benzyloxycarbonyl-2-amino-4-Pentenoyl)-L-valine benzyl ester
C=CCC(NC(=O)OCc1ccccc1)C(=O)N[C@H](C(=O)OCc1ccccc1)C(C)C
cyanomethyl ester

Reagenzien

Keine

Lösungsmittel

CN(C)C=O
DMF
C1CCOC1
THF

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Vorschrift

N-(4-pentenoyl)valyl-pdCpA was prepared. Treatment of S-valine methyl ester with 4-pentenoic anhydride afforded the respective amide as a colorless oil in 73% yield. Following hydrolysis of the ester moiety (LiOH, aq THF), the derived intermediate was converted to the respective cyanomethyl ester (4). Admixture of 4 and pdCpA Robertson, et al., Nucleic Acids Res. 17:9649 (1989), in freshly distilled DMF afforded N-(4-pentenoyl)valyl-pdCpA (5) as a colorless solid in 94% yield. A sample of N-(2-nitroveratryloxycarbonyl)valyl-pdCpA was prepared as described, Robertson, et al., J. Am. Chem. Soc. 113:2722 (1991) for comparative purposes.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US06245938B1uspto-grants-2001_06