A metal-free chemodifferentiating A2BB' 4CR manifold for the modular synthesis of tertiary skipped diynes is described. The manifold performs a triethylamine triggered reaction of alkyl propiolates and acid chlorides to assemble two units of each component in the form of two propargylic alkynoates, a tertiary alcohol, and an ester. A differentiated incorporation of the two acid chloride components ensures functional diversity in the final structure. In addition, the presence of two connected propargylic alkynoates provides a reactive platform for complexity generation.