A series of 1,4-thiazepanes were synthesized using gold-catalysis from 1,3-aminothioethers having two or three carbon stereocenters. The process consists in a 7-exo-dig cyclization with CÀ S bond formation and concomitant allyl S-to-C migration, which occurs intramolecularly as demonstrated by a cross-over experiment. X-ray crystal-structure analysis of one product confirmed the expected stereochemistry. Two examples of reactions, azide-alkyne cycloaddition (CuAAC) and N-alkylation, illustrate the potential postfunctionalization of the synthesized 1,4-thiazepanes. Finally, the N-propargyl 1,4-thiazepanes underwent a sulfur-assisted 1,6-enyne cycloisomerization, which led through a 6-exo-dig cyclization to N,Sheterobicyclo[4.3.1] systems with a bridgehead double bond.