Nitrate esters alkoxy radicals from

Scission of alkoxy radicals (12) generated from nitrate esters and BU3S11H furnish a-amino acid radicals (13) (Scheme 4). This new method for forming a-amino acid radicals may be useful for generating site-specific radicals in peptides.25 The reactions of C(2) glyceryl radicals (14) have been observed by EPR. Whereas the phosphate derived radical (14a) gave the reduced product (15a) in 70% yield, the unsubstituted... 

Side-chain halogenated amino acid derivatives are reduced, deuterated, allylated and alkylated with stannanes and related reagents in free-radical processes [53]. Other side-chain functional groups may also be manipulated to produce amino acid radicals [8, 54-58], and, in particular. Barton decarboxylation of aspartate and glutamate derivatives has been applied in this manner (Scheme 8) [55]. Related procedures have been developed to generate amino acid radicals by dehydrox-ylation of hydroxy amino acid derivatives [56]. Hydroxy amino acid derivatives may also be converted to nitrate esters, from which the corresponding alkoxy radi-... 

In an analogous manner to the development of decomposition pathways for nitramines, estimates can be made for the decomposition pathways of other classes of energetic materials. For instance, nitrate esters will first break off an NO2 group. From Tables IV and V, one concludes that the resulting alkoxy radical will readily decompose to form an aldehyde, with the subsequent radical eliminating a nitro group, forming another aldehyde. 

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