A simple catalyst system generated in situ by combination of 5 mol-% [Zr(NMe 2 ) 4 ] and 10 mol-% of a sulfonamide catalyzes the intermolecular hydroamination of alkynes with primary amines. At elevated temperatures, hydroamination is achieved with both internal and terminal alkynes as well as with sterically demanding and less demanding primary amines. In contrast, secondary amines do not react under identical conditions. Of the sulfonamide additives investigated, sterically demanding tosylamides such as N-(tertbutyl)-p-toluenesulfonamide give the best results. The re-
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