Cadiot–Chodkiewicz coupling

Cadiot–Chodkiewicz coupling
Named after Paul Cadiot
Wladyslav Chodkiewicz
Reaction type Coupling reaction
Identifiers
Organic Chemistry Portal cadiot-chodkiewicz-coupling
RSC ontology ID RXNO:0000100

The Cadiot–Chodkiewicz coupling in organic chemistry is a coupling reaction between a terminal alkyne and a haloalkyne catalyzed by a copper(I) salt such as copper(I) bromide and an amine base.[1][2] The reaction product is a di-acetylene or di-alkyne.

The reaction mechanism involves deprotonation by base of the acetylenic proton followed by formation of a copper(I) acetylide. A cycle of oxidative addition and reductive elimination on the copper center then creates a new carbon-carbon bond.

Related couplings are the Glaser coupling and the Eglinton coupling.

Scope

In one study[3] the Cadiot–Chodkiewicz coupling has been applied in the synthesis of acetylene macrocycles starting from cis-1,4-diethynyl-1,4-dimethoxycyclohexa-2,5-diene. This compound is also the starting material for the dibromide through NBS and silver nitrate:

The coupling reaction itself takes place in methanol with piperidine, the hydrochloric acid salt of hydroxylamine and copper(I) bromide.

See Also

References

  1. Chodkiewicz, W. Ann. Chim. Paris 1957, 2, 819–69.
  2. Cadiot, P.; Chodkiewicz, W. In Chemistry of Acetylenes; Viehe, H. G., Ed.; Marcel Dekker: New York, 1969; pp 597–647.
  3. Bandyopadhyay, Arkasish; Varghese, Babu; Sankararaman, Sethuraman. "Synthesis of 1,4-Cyclohexadiene-Based Acetylenic Macrocycles with Cadiot−Chodkiewicz Coupling. Structure of a Tub-Shaped Tetrameric Container". The Journal of Organic Chemistry 71 (12): 4544–4548. doi:10.1021/jo0605290.
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