Arylamide ions

The study of the ablation of arylamide ions prior to 1987, in similar fashion to that of the analogous reaction with aryloxides discussed above, gave little promise of synthetically useful reactions. In Kim and Bunnett s original papers on the SrnI reaction,1 they reported that the anilide ion (PhNH ) behaves... 

Fig. 4.8. Formation of mutagenic N-hydroxyamines from arylamides. Pathway a via deacetylation and subsequent IV-hydroxylation. Pathway b via IV-hydroxylation and subsequent deacetylation. Pathway c via N-acetoxy arylamine produced by IV,0-acyltransferases. [99]. Activation of hydroxylamines and hydroxylamides by O-sulfation is not shown. In all cases, the ultimate electrophile may be a nitrenium ion.

This zinc-dependent enzyme [EC 3.4.11.1], also referred to as cytosol aminopeptidase, leucyl aminopeptidase, and peptidase S, catalyzes the hydrolysis of a terminal peptide bond such that there is a release of an N-terminal amino acid, Xaa-Xbb-, in which Xaa is preferably a leucyl residue, but may be other aminoacyl residues including prolyl (although not arginyl or lysyl). Xbb may be prolyl. In addition, amino acid amides and methyl esters are also readily hydrolyzed, but the rates with arylamides are exceedingly slow. The enzyme is activated by heavy metal ions. 

Lyotropic liquid crystalline properties were observed for poly (arylamide) monodendrons derived from 1,3,5-substituted amino acid chloride hydrochlorides according to Kim [168]. These systems aggregate readily to form high molecular weight species in the absence of complexing ions. Amide solvents containing more than 40 wt.% of the dendrons exhibit nematic phase liquid crystalline texture under a polarizing microscope, whereas, 60 wt.% solutions produce a hard gel under static conditions. 

These last two studies led us to investigate the possibility of using halonium ions to mediate the reactions of simple alkyl and arylamides with glycals. 

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