Azides reaction with amides

Dinitrogen monoxide can act as a Lewis base in complexes (monodentate in [Ru(NH3)5(N20)] +). It can also act as a Lewis acid with strong Lewis bases, for example, in the reaction with amides to form azides. 

AHf of metal silicides 5.10.3.2.1 Thiocarbonyl complexes formation 5.8.2.13.1 Tin amides reactions with metal carbonyls 5.S.5.4.3 Tin azides reactions with... 

The commonest of these for oxirane opening are amines and azide ion [amide ions promote isomerization to allylic alcohols (Section 5.05.3.2.2)]. Reaction with azide can be used in a sequence for converting oxiranes into aziridines (Scheme 49) and this has been employed in the synthesis of the heteroannulenes (57) and (58) (80CB3127, 79AG(E)962). 

Figure 5.22 The NHS ester of ANB-NOS reacts with amines to form amide bonds. Subsequent photoactivation of the complex with UV light causes phenyl azide ring expansion and reaction with neighboring amines.

Figure 18.11 NHS-PEG4-azide can be used to modify an amine-containing molecule to create an amide derivative terminating in azido groups. The azide modifications then can be used in a click chemistry reaction that forms a triazole linkage with an alkyne-containing molecule. Alternatively, the azide derivative can be used in a Staudinger ligation reaction with a phosphine derivative, which results in an amide bond linkage.

Ar-Acyl oxy- A -a 1 k oxyamides have been found to undergo SN2 reactions with a number of organic and inorganic nucleophiles including anilines, thiols, hydroxide and azide anions. Reaction products from all of these processes are themselves reactive anomeric amides and outcomes have uncovered novel chemistry of this unusual class of compounds. 

The Ea for azide reaction on A-formyloxy-A-m< //n7formamide was 22.2 kcal mol-1 higher than reaction with the A-methoxy model. A similar result was obtained to the reactions of ammonia and reinforces the activating influence of /V-alkoxy groups upon SN2 reactions in anomeric A-acyloxy-A-alkoxy amides. 

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