Addition trimethylsilylazide

Addition of thiophosgene to the reaction mixture of ImCSIm and trimethylsilylazide causes the yield to become quantitative.11301,11323 In the conversion with trimethylsilyl azide the required ImCSIm could also be made in situ from trimethylsilylimidazole and thiophosgene, giving the thiatriazoles in 70—80% yield.11321... 

A flask was charged with the eatalyst from Step 2 (42 mg) and 1 ml diethyl ether. 1,2-Meso cyclopentane epoxide (0.060 mmol) was added and the mixture stirred 15 minutes at which time trimethylsilylazide (3.15 mmol) was added and the mixture stirred an addition 28 hours. Thereafter, the solution was concentrated and the residue filtered through a 10 ml plug of silica gel with 5% to 20% EtOAc/hexanes mixture. Desilylation was performed by dissolving the purified intermediate into 5 ml methyl alcohol to which was added (lS)-(+)-10-camphorsulfonic acid (0.15 mmol), the mixture stirred 30 minutes, purified by flash chromatography, and the product isolated in 80% yield, 94% ee. 

This class is illustrated by some silylated derivatives, Me3SiN=PPh2-NR -PPh2 with R = Et, -Pr, -Bu, prepared from Ph2PNR PPh2 with trimethylsilylazide (Scheme 42). Theses compounds can be readily undergo oxidative addition of snlfur and selenium to the P(III) site and react with... 

Addition reactions of low coordinate phosphorus compounds have proved to be an interesting route to novel acyclic phosphazenes. Phosphino carbenes, R2PCSiMej, exhibit typical multiple bond behavior in 2+3 cycloaddition reactions with trimethylsilylazide. The cycloadduct easily rearranges to the diazo derivatives R2P(=NSiMe3) C (=N2) SiMej. The addition of the... 

Similarly, [1 + 2]-cycloaddition of sulfur to methylene(imino)phosphoranes 5 leads to 2-imino-1,2A5-thiaphosphirancs 6 (route A in Scheme 3), obtained also by trimethylsilylazide or iert-butylazide addition to methylene(thioxo)phosphiranes followed by thermal decomposition of intermediate A1 -triazaphospholcncs 7 (route B in Scheme 3) [19], It should be noted that the photochemical decomposition of A1 -triazaphospholcncs 7 results in an alternative structure with ring nitrogen atom, 2-thio-l, 2-A5-azaphosphiranc 8 (route C in Scheme 3) [19],... 

Recent advances in the Staudinger reaction of tertiary phosphines with azido compounds have been reviewed.The reaction of the alkynylphosphine (88) with phenylazide yields the unstable intermediate (89), which in the presence of protic substances undergoes nucleophilic addition to the triple bond. The reactivity of the nitrogen-silicon bond of the phosphinimine derived from triphenylphosphine and trimethylsilylazide has been exploited in reactions with chloroformyl reagents to generate new functionalised phosphinimines, e.g., (90). ... 

The addition of trimethylsilylazide to the carbon-carbon triple bond (Eq. 4) is attractive both for safety and for the ease of removing the silyl group. ... 

An impressive array of methods has been applied to the preparation of 4-phenyl-1,2,3-triazole (1.3-4) the standard trimethylsilylazide (Eq. 29), sodium azide (Eq. 31), and hydrazoic add additions. But, in addition to these well-documented techniques tosylazide addition (Eq. 32) intramolecular cyclization (Eq. 33), triphenylphosphonium salt addition (Eq. 34), addition to styrenes bearing strong electron-withdrawing -groups... 

The addition of azide ion, arylazides, and trimethylsilylazide to acetylenes have all been carried out in good-to-excellent yield (Eqs. The... 

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