Azides, amides from

Triazoles have also been obtained when the carbon atom adjacent to the activated methylene group carries a nitrogen function (i.e., amides, nitriles, amidines, and imines - ). In many of these cases it is impossible to decide, without N-labeling experiments, whether the third nitrogen of the triazole ring is derived from the toluene-p-sulfonyl azide or from the activated methylene compound. With amides, amidines, and nitriles, the first possibility seems more reasonable, but with imines, the third nitrogen is that of the imino group (Scheme... 

A-Acyloxy-A-alkoxyamides undergo Sjv2 reactions with a number of organic and inorganic nucleophiles including anilines, thiols, hydroxide and azide. Products from all of these processes are themselves anomeric amides, which undergo secondary reactions. 

The elegant asymmetrization methodology of a meso compound, achieved in high enantioexcess under chiral environment, was the highlight of the total synthesis of (+)-pancratistatin (94) reported by Trost and Pulley (31]. The synthesis commenced with ( )-conduritol-A (130), obtained from p-benzoquinone, (Scheme 18) which was converted into the acetonide 131 and thence, via the dialkoxide to the cis-bis carbonate 132 (Scheme 19). The chiral n-ailyl palladium complex A formed on treatment erf 132 with the catalyst generated from chiral bis-amide 133 and n-allyl palladium chloride underwent azide substitution from the less hindered face of the molecule to provide the monocarbonate 134 in excellent yield and with high optical induction. 

Scheme 2. Pathways for the formation of the hafnium amides from azides and hafnium hydrides. Reprinted with permission from Organometallics 1, 1025. Copyright (1982) American Chemical Society.

Non-acidic functional replacement analogues are named by replacing the word acid with the appropriate class name occurring earliest in the following list hydrazide, halide, azide, amide, cyanide, nitride, imide. Other replacing groups are denoted by infixes, as described earlier for acidic functional replacement analogues. The examples below are derived from phosphoric acid. 

Oxophilic early transition metal Lewis acids were shown to react differently from azaphilic Lewis acids when ring-opening of acylaziridines was attempted [21], When A -acyl aziridine 48 was treated with trimethylsilylazide in the presence of a catalytic amount of Cp2Zr(SbF6)2, the product was azide-amide 49, whereas in the presence of Cu(OTf)2 the ring-expansion product, oxazoline 51, was formed (Sch. 1). 

Maunier, V, Boullanger, P, Lafont, D, A one-pot synthesis of glycosyl amides from glycosyl azides using a modified Staudinger reaction, J. Carbohydr. Chem., 16, 231-235, 1997. 

Tetrakis(dimethylamino)titanium is a useful reagent for preparing amidines from secondary amides. From A X-thionyldiimidazole and secondary amides of boA aromatic and aliphatic carboxylic acids amidines (313 Scheme 50) are formed under mild conditions in moderate to good yields. N-Tosyl-amidines (314) can be obtained by reacting secondary thioamides (aliphatic and aromatic) with tosyl azide. Thiobenzamides have been condensed with anilines to afford amidines (315). Thioamides can be converted to amidines, e.g. (316), by treatment with ammonia in the presence of mercury acetate. ... 

Lysergic Acid Azides and Amides from Lysergic Acid Hydrazides... 

The crystal chemistry of solid inorganic nitrides, azides, amides and imides is reviewed systematically. Many of the structures unique to nitrides are illustrated and analyzed. We give full crystallographic data for all compounds with well determined structures and list derived bond valences and Madelung potentials. Similarities to and differences from oxide chemistry are pointed out and general principles relating to structure and bonding in nitrides are elucidated. 

The Ru(III)-promoted formation of the amide bond permits the synthesis of amides from azides and thio acids at room temperature, and the reaction is applicable to less-reactive azides. Thus the azide, 119 as a model compound, in methanol solution, was transformed in 80% yield into the corresponding acetamide 240 by the action of thioacetic acid (2.5 eq.) and 2,6-lutidine. ... 

Irradiation isopropanol Sulfonic acid amides from sulfonic acid azides... 

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