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Updated: May 12, 2026

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
Published on: February 16, 2020
Enabling Base-Free Direct C-H Arylation of Thiophene Derivatives: Glycerol-Derived Solvents as Active Reaction Media
Sara Gracia-Barberán1,2, Stefano Nejrotti3,4,5, Alejandro Leal-Duaso1,2
1Instituto de Síntesis Química y Catálisis Homogénea (ISQCH-CSIC), Faculty of Science, University of Zaragoza, Zaragoza, Spain.
Abstract:
Nonvolatile glycerol derivatives are employed as effective reaction media for the Pd-catalysed direct CH arylation of 3,4-ethylenedioxythiophene and other thiophenes. The thoughtful design of noninnocent glycerol-derived ionic liquids (ILs) allows them to act simultaneously both as solvent and base, eliminating the need for an additional base and thus improving the sustainability of the process. Moreover, the stabilization of palladium nanoparticles in the task-specific solvent offers an excellent approach by providing the advantages of a homogeneous, selective, and recoverable catalytic system. This multifunctional behaviour highlights the potential of glycerol-derived ILs as sustainable solvents and promoters for transition metal-catalysed CH activation reactions.
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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.
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.
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.
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.
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.
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3