Background: Transition metal-catalyzed reactions of alkynyl halides are a
versatile means of synthesizing a wide array of products. Their use is of particular interest
in cycloaddition reactions and in constructing new carbon-carbon and carbon-heteroatom
bonds. Transition metal-catalyzed reactions of alkynyl halides have successfully been
used in [4+2], [2+2], [2+2+2] and [3+2] cycloaddition reactions. Many carbon-carbon
coupling reactions take advantage of metal-catalyzed reactions of alkynyl halides,
including Cadiot-Chodkiewicz, Suzuki-Miyaura, Stille, Kumada-Corriu and Inverse
Sonogashira reactions. All the methods of constructing carbon-nitrogen, carbon-oxygen,
carbon-phosphorus, carbon-sulfur, carbon-silicon, carbon-selenium and carbon-tellurium
bonds employed alkynyl halides.
Objective: The purpose of this review is to highlight and summarize research conducted in transition metalcatalyzed
reactions of alkynyl halides in recent years. The focus will be placed on cycloaddition and coupling
reactions, and their scope and applicability to the synthesis of biologically important and industrially relevant
compounds will be discussed.
Conclusion: It can be seen from the review that the work done on this topic has employed the use of many
different transition metal catalysts to perform various cycloadditions, cyclizations, and couplings using alkynyl
halides. The reactions involving alkynyl halides were efficient in generating both carbon-carbon and carbonheteroatom
bonds. Proposed mechanisms were included to support the understanding of such reactions. Many
of these reactions face retention of the halide moiety, allowing additional functionalization of the products,
with some new products being inaccessible using their standard alkyne counterparts.