1Introduction Ynamines [1-aminoalkynes, or N-alkynyl amines] have endured through two contrasting phases in the last four decades. First, they enjoyed a phase of synthetic eminence after the establishment of a practical synthesis in 1963. In the ensuing twenty years, ynamines became one of the most synthetically useful subgroups of alkynes utilized in countless creative work by many synthetic chemists. Reactivities of 1-aminoalkynes were thoroughly explored. However, unlike its close relative enamines, this prominent period did not last. The extent of synthetic application of ynamines has suffered a dramatic decline during the last twenty years. This decline characterizes the second phase of ynamines. The limited synthetic application of ynamines is largely due to the difficulties in preparation and handling of ynamines. Their sensitivity toward hydrolysis and their high reactivity render ynamines synthetically inaccessible in diversity.