Cadiot-Chodkiewicz Coupling Reaction

The Cadiot-Chodkiewicz coupling refers to the catalytic coupling of a terminal alkyne with a haloalkyne in the presence of a copper(I) salt (e.g., cuprous chloride or cuprous bromide) and a base to yield a diyne derivative. This reaction was discovered by Paul Cadiot and W. Chodkiewicz and is named after them.

The Cadiot-Chodkiewicz coupling exhibits high selectivity and reactivity, providing an efficient strategy for synthesizing functionalized alkyne compounds. It is widely applied in organic synthesis, particularly in the construction of complex molecular architectures and polyyne structures.

Reagents: Copper(I) salt, base
Reactants: Terminal alkyne, haloalkyne
Products: Diyne derivatives
Reaction Type: Coupling reaction

Experimental Tips:

• Common solvents include methanol, ethanol, DMF, THF, and water.

• Frequently used bases: ammonia, primary amines, pyridine, and piperidine.

• In addition to simple Cu(I) salts, supported copper catalysts such as Cu(I)-zeolites are also effective. These catalysts can be recycled and reused, enhancing the reaction's economic viability and sustainability.

Reaction Mechanism:
The reaction proceeds via copper(I)-acetylide formation from the terminal alkyne, followed by oxidative coupling with the haloalkyne to form the diyne product.

Original Literature: Paul Cadiot, W. Chodkiewicz. Bulletin de la Société Chimique de France. 1957, 875-882.

Popular Applications: Synthesis of a Wheel-Shaped Nanographdiyne. J. Am. Chem. Soc. 2023, 145(9), 5400–5409. Recent developments and applications of the Cadiot–Chodkiewicz reaction. Org. Biomol. Chem. 2015, 13, 6891-6905. Bulky Trialkylsilyl Acetylenes in the Cadiot−Chodkiewicz Cross-Coupling Reaction. J. Org. Chem. 2002, 67(19), 6841-6844.