Amines azidotrimethylsilane

For the azide cleavage of chiral 2,3-epoxy diester 3, the submitter s earlier procedure81 was modified to reduce the amount of azide reagent (azidotrimethylsilane, TMSN3) and lower the reaction temperature. This effort, coupled with the submitter s recent finding that such a reaction can be accelerated in the presence of amines,89,9 led to the use of the system described above. The reaction may proceed by way of the... 

Recently, " a novel and convenient one-pot synthesis of 8-(arylamino)theophyllines starting from l,3-dimcthyluracil-6-amine through reaction, successively, with phosgeniminium chloride, azidotrimethylsilane and arylamines, has been reported, e.g. formation of 8-anilino-theophylline (16)." ... 

Primary alkyl amines. a-Alkoxy azides are reduced to primary amines by lithium aluminum hydride in ether. A side reaction noted occasionally, reduction to an ether, can be suppressed by addition of TMEDA. Sodium bis(2-methoxy-ethoxy)aluminum hydride cannot replace lithium aluminum hydride in this reductive amination. The a-alkoxy azides are available by reaction of aldehydes with azidotrimethylsilane, by addition of hydrazoic acid to an enol ether, or by reaction of ketals with the l8-crown-6 complex of sodium azide. 

Azanaphthalene iV-oxides undergo photochemical deoxygenation reactions in benzene containing BF3 OEt2, resulting in amines in 70-80% yield these amines are important in the synthesis of heterocyclic compounds. Azidotrimethylsilane reacts with traws-1,2-epoxy alky Isilanes in the presence of BF3-OEt2 to produce (Z)-l-alkenyl azides. The cis-1,2-epoxyalkylsilanes undergo rapid polymerization in the presence of Lewis acids. 

TfOH catalyzes the amination and phenylamination of aromatics via the corresponding aminodiazonium ion generated from azidotrimethylsilane and phenyl azide respectively (eq 19). 

Keywords Methyl levulinate, primary amines, isocyanides, azidotrimethylsilane, methanol, dichloromethane, room temperature, one-pot, two-step synthesis, Ugi reaction, 1,5-disubstituted tetrazoles, his-pyrrolidinone tetrazoles... 

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