Bis(4-nitrophenyl) Carbonate

[5070-13-3]  · C13H8N2O7  · Bis(4-nitrophenyl) Carbonate  · (MW 304.22)

(peptide coupling reagent;1 reagent for formation of carbamate linked cytosines2)

Physical Data: mp 144-145 °C.

Solubility: sol chloroform and THF.

Form Supplied in: off-white powder.

Peptide Coupling Reagent.

N-Protected amino acids can be converted into activated 4-nitrophenyl esters suitable for peptide coupling reactions. Reaction of the N-protected amino acid in acetic acid and pyridine with 1.5 equiv of the reagent under reflux for 3 h affords the activated ester following loss of CO2 from the intermediate mixed anhydride (eq 1).1

Formation of Carbamate-Linked Cytosine Oligomers.2

Reaction of the 5-protected aminocytosine derivative (1a) with the reagent in DMF and Et3N afforded an activated 4-nitrophenyl carbonate derivative. Following purification, reaction of this compound with another monomer unit, (1b), provided the linked dimer (2) (eq 2). This compound was elaborated further into a carbamate-linked hexameric cytosine oligomer which was found to conjugate strongly to native DNA strands.

Formation of Ureido Sugars.3

A variety of 2-amino sugars can be converted into ureido derivatives in reasonable yields (50-83% for two steps). For example, methyl 3,4,6-tri-O-acetyl-2-amino-2-deoxy-b-D-glucopyranoside is first reacted with the reagent to afford a 4-nitrophenyl carbamate intermediate which, upon further reaction with a variety of secondary amines in CH2Cl2 at room temperature for 5-24 h, provides the ureido sugar. In a similar manner, symmetrical and unsymmetrical N,N-disubstituted ureas can be prepared by the sequential addition of amines to the reagent.4

1. (a) Wieland, T.; Heinke, B.; Vogeler, K.; Morimoto, H. LA 1962, 655, 189. (b) Glatthard, R.; Matter, M. HCA 1963, 46, 795.
2. Stirchak, E. P.; Summerton, J. E.; Weller, D. D. JOC 1987, 52, 4202.
3. Piekarska-Bartoszewicz, B.; Temeriusz, A. Carbohydr. Res. 1990 203, 302.
4. Izdebski, J.; Pawlak, D. S 1989, 423.

Eric D. Edstrom

Utah State University, Logan, UT, USA

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