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Updated: Oct 12, 2025

Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
Recent advances in Cu-catalyzed transformations of internal alkynes to alkenes and heterocycles
Javeed Ur Rasool1, Asif Ali2, Qazi Naveed Ahmad3
1Natural Product and Medicinal Chemistry Division, CSIR-Indian Institute of Integrative Medicine, Canal Road, Jammu-180001, India.
Abstract:
Numerous metal-catalyzed reactions involving internal alkynes and aimed towards synthetically and pharmacologically important alkenes and heterocycles have appeared in the literature. Among these, Cu-catalyzed reactions have a special place, which has prompted the investigation and development of carbon-carbon and carbon-heteroatom bond-forming reactions. These reactions possess wide scope, and during the paths of these reactions, either stable or in situ intermediates are formed via the addition of Cu as a core catalyst or synergistic catalyst. In this review, we aim to report different contributions relating to Cu-catalyzed reactions of internal alkynes for the synthesis of different valuable alkenes and heterocycles which have appeared in the literature in the last decade. We anticipate that this appraisal will deliver basic insights for the further advancement of Cu-catalyzed reactions in organic chemistry.
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Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Preparation of Alkynes: Alkylation Reaction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Preparation of Alkynes: Dehydrohalogenation
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

