COPPER(I) SUBSTITUTIONS . SCOPE AND MECHANISM OF CUPROUS ACETYLIDE SUBSTITUTIONS

Substitutions with cuprous acetylides provide a most convenient route to a wide variety of acetylenes and heterocyclic arrays. This summarizing work casts these reactions into a general pattern for copper(I) substitution. The reactivity of acetylides toward bond type, the kinetics of aromatic substitution, the geometry of allylic substitution, the nature and path of the heterocyclic synthesis, and some mechanistically instructive ring size experiments are presented. Additional heterocyclic syntheses are described. The mechanisms for reaction range from a four center process (aryl halide substitution) to homolytic scission (oxidation with N-bromosuccinimide). The stereochemistry of the cuprous chloride-catalyzed hydrolysis of allylic halides is portrayed and the reaction of these salts with halohydrins is described. © 1969, American Chemical Society. All rights reserved.