1-Sulfonyl-1,2,3-triazoles undergo a Doyle-Kirmse reaction upon treatment with allylic sulfides in the presence of a rhodium(II) catalyst to afford alpha-allyl-alpha-sulfanylimines. Terminal alkynes are regioselectively multifunctionalized by the introduction of C-N, C-S, and C-C bonds through a one-pot sequence consisting of a [3 + 2] dipolar cycloaddition reaction with azide and subsequent Doyle-Kirmse reaction.