Indium(III) triflate catalyzed tandem azidation/1,3-dipolar cycloaddition reaction of ω,ω-dialkoxyalkyne derivatives with trimethylsilyl azide

The azidation reaction of dialkyl acetal derivatives with trimethylsilyl azide (TMSN3) was efficiently catalyzed by 1-5 mol % of In(OTf)(3). The major product differed depending on the substrate structure and molar ratio of TMSN3, that is, aliphatic acetals provided alpha-azido ether derivatives, while aromatic acetal (benzaldehyde dimethyl acetal) provided gem-diazide, respectively. Furthermore, novel tandem azidation/1,3-dipolar cycloaddition reaction using alkynyl acetal derivatives gave bicyclic triazolo-heterocyclic compounds, recognized as chemically modified aza-sugar analogues, in high yields under mild conditions. (c) 2005 Published by Elsevier Ltd.