Propargyl silanes with a terminal alkyne moiety undergo a 1,2-silyl shift when activated with electrophiles such as H+, Br+, I+, and PhSe+. A method was developed to trap 1,3-transposed electrophilic centers with various internal O-, N-, and S-nucleophiles in a 5-exo manner. This synthetic procedure provided five-membered heterocycles containing a trisubstituted olefin side chain. The scope of the method includes access to tetrahydrofuran, γ-butyrolactone, 2-isooxazoline, pyrrolidine, and thiolane derivatives in yields ranging from 25 to 85% (23 examples in total). Reactions with TsNBr2 ensured complete (E)-selectivity of the newly formed olefins. Further functionalization of the obtained 1-trialkylsilyl-2-bromovinyl side chain was demonstrated by double-bond geometry-preserving electrophilic substitution and cross-coupling reactions that provided heterocycles with a trisubstituted vinyl moiety.