Recent developments and applications of the Cadiot–Chodkiewicz reaction

Abstract

The classical heterocoupling of a 1-haloalkyne with a terminal alkyne catalyzed by copper salts in the presence of a base for the synthesis of unsymmetrical diynes is termed the Cadiot-Chodkiewicz coupling reaction. The diynes are of great importance due to their biological, optical and electronic properties. A number of modifications have been developed recently to improve the efficiency of Cadiot-Chodkiewicz coupling reactions in terms of selectivity and yield. This is the first review on the Cadiot-Chodkiewicz cross-coupling reaction which highlights the modern approaches and protocols developed for the synthesis and applications of unsymmetrical 1,3-diynes.

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

“…[199] In such cases, the selectives ynthesis of unsymmetrical 1,3-diynes can be achieved by starting from at er-minal alkyne and an alkynyl hypervalent iodine reagent (Scheme 27). [205] The reaction proceeds under mild conditions with good efficiency,affords high selectivity,a nd has an excellent substrate scope. [205] The reaction proceeds under mild conditions with good efficiency,affords high selectivity,a nd has an excellent substrate scope.…”

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

“…A milder transformation withoutt ransition metal reagents is awaited.Aless-strained tetrayne-containing macrocycle could be obtained by Glaser coupling (Figure 4a). This implies that other Glaser-type methods, such as Eglinton, Hay,a nd Cadiot-Chodkiewiczc ouplings, [51][52][53][54] will be applicable to angle-strained oligoyne-containingm acrocycles.…”

One‐Pot Synthesis of Unsymmetrical 1,3‐Butadiyne Derivatives and their Application in the Synthesis of Unsymmetrical 2,5‐Diarylthiophenes

“…On the other hand, Cadiot–Chodkiewicz coupling has been widely used to synthesize unsymmetrical 1,3‐butadyines . This consists of a cross‐coupling reaction of terminal acetylenes with 1‐haloalkynes, using copper and suitable amines.…”

“…The advantages of this reaction are good yields, a variety of substrates, mild conditions, and the low cost of the catalysts. However, the electronic properties of terminal acetylenes and haloalkyne substituents can affect the selectivity of the reaction, with the formation of homocoupling by‐products that complicate the purification of the unsymmetrical 1,3‐butadyines, leading to a decrease in yields , . Variations of the Cadiot–Chodkiewicz reaction were described by Wang et al, employing CuI (10 mol‐%)/P( o ‐Tol) 3 /K 2 CO 3 and EtOH as a solvent.…”