Organoazides

Reichle, W. T. Preparation, Properties, and Thermal Decomposition Products of Organoazides of Silicon, Germanium, Tin, Lead, Phosphorus, and Sulfur. Inorg. Chem. 3, 402 (1964). 

Monomeric compounds (x = 1) containing M=E double bonds remained unknown until Power and Roesky et al. reported in 2001 on the synthesis of the first monomeric iminoalane and -gallane by oxidative addition of an organoazide to a sterically encumbered low-valent A1(I) compound 4 This reaction type has been shown previously to yield heterocyclic compounds by use of sterically less hindered [Cp Al]4.145 Very recently, von Hanisch and Hampe synthesized the first GaAs compound featuring a Ga=As double bond5 (Scheme 19, Figs. 41 and 42). 

Organoantimony ligands, coordination compounds with, 95-131 Organoazides, 292, 293 Oxabetaines, 37, 64-66 Oxidation, 4... 

Recent investigations into the reactivity of 32 with organoazides have led to the formation of amido and imido complexes. Reaction of 32 with... 

Aryne generation. The desilylative route (e.g., by CsF) is the most expedient method for generation of arynes. 1,2-Functionahzation of arenes from 2-trimethylsilylaryl triflates is readily achieved as long as noninterfering co-reactants are used. Thus trapping by organoazides leads to benzotriazoles, by phenyhodonium diacyhnethyhdes leads to... 

Glaser coupUng of l-aUcynes followed by [3+2]cycloaddition with organoazides affords bi-5,5 -triazolyls. Achieved in one step with Cu and CUSO4 in the air, the reaction is particularly favored by adding Na2C03. ... 

Addition and cycloaddition. Two slightly different protocols are available for achieving addition of 1-alkynes to trifluoromethyl ketones use either CuOTf and t-BuOK with Xantphos in THF at 60°, or Cu(OTf)2 and two equivalents of t-BuOK and 1,10-phenanthro-line in toluene at 100°. Cyanoformate esters can contribute the CN group as an addend to react with organoazides in a [3+2]cycloaddition catalyzed by CuOTf. ... 

Alkynylmagnesiumbromides add to organoazides to form4-(l,2,3-triazolyl)magnesium bromides. 1,4,5-Trisubstituted 1,2,3-triazoles are obtained after transmetallation (ZnCy and Negishi coupling. 

Cycloaddition. The title complex is found useful as catalyst for the cycloaddition of organoazides to 1-aIkynes to form 1,5-disubstituted l,2,3-triazoles. ... 

Organoazides are reduced by Zn-NH4C1 in hot aqueous EtOH and react with 3-keto esters in situ to give p-amino-a,(3-unsaturated esters. ... 

Boron trichloride. 13, 43 14, 54 15. 44 Activation of boronic acids. Alkyl ranes, as reactive intermediates. For eu azacycles (azetidines, pyrrolidines, pipen erocycle synthesis involves reaction of a I organoazide. 

Indolines. Nickel complexes mediate h organoazides, resulting in indolines. 

Reduction of N-X bonds. Both aliphatic and aromatic organoazides " are readily... 

Organoazides from primary amines The diazo transfer is catalyzed by CuSO. Free hydroxyl groups do not disturb this reaction. 

Organoazides. Alkyl azides are obtain by using the MejSiNj-Bu NF reagent systen corresponding bromo derivatives in a reactioa A cyclic allylic azide is required for a synd is obtainable from a Pd-catalyzed reaction of dicarbonate in the presence of a chiral ligand... 

Organoazides. Alkyl azides are obtained by a displacement reaction of alkyl halides by using the McjSiNj-Bu jNF reagent system. 2-Azidoimidazoles are obtained from the corresponding bromo derivatives in a reaction catalyzed by (PhjPjjPdClj. ... 

By having a carbanionoid center, diazo compounds react with boranes easily. For example, diazoketones yield -oxoboranes which rearrange in situ to generate enol borates (26-28). The use of organoazides instead of diazo compounds leads to secondary amines (29, 30). 

Cundari and coworkers have also demonstrated for the first time that it is possible to stabilize organoazide complexes of gold(I) f Scheme 4.151. They have found that the N2 expulsion from... 

Brill et al. [376,380] have illustrated the application of T-jump/FTIR spectroscopy with rapid thermolysis of various organoazide polymers and hydroxyl-terminated polybutadiene with and without Ti02 and melamine additives. The T-jump/FTIR technique determines the chemistry of fast pyrolysis. 

As outlined by the corresponding mesomeric formnlae shown in Scheme 12.1 organoazides are able to provide free electron pairs for the formation of metal complexes too. 

For a deeper understanding of the donor properties of organoazides, quantum chanistry can help. Calculation of methyl azide and its addncts to a lithium cation by MP2/6-311G results the structural parameters and charge distributions presented in Figure 12.1 and Table 12.1. 

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