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Updated: Dec 30, 2025

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
Alkynes as Privileged Synthons in Selected Organic Name Reactions.
Majid M Heravi1, Mahzad Dehghani1, Vahideh Zadsirjan1
1Department of Chemistry, School of Science, Alzahra University, Vanak, Tehran, Iran.
Alkynes are versatile building blocks in organic chemistry, widely used in name reactions like the Click and Sonogashira reactions. This review highlights their role as privileged synthons in synthesizing complex molecules and heterocycles.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
- Medicinal Chemistry
Background:
- Alkynes are fundamental unsaturated hydrocarbons featuring at least one carbon-carbon triple bond.
- They serve as crucial synthons and molecular scaffolds in organic synthesis, enabling the construction of reactive motifs.
- Terminal alkynes are particularly valuable in synthetic strategies.
Purpose of the Study:
- To review the applications of alkynes as privileged synthons in prominent organic name reactions.
- To underscore the utility of alkynes in the synthesis of heterocycles and complex organic molecules.
- To highlight the role of alkynes in reactions such as the Huisgen 1,3-dipolar cycloaddition (Click reaction), Sonogashira reaction, and Hetero Diels-Alder reaction.
Main Methods:
- Literature review focusing on established name reactions involving alkynes.
- Analysis of alkyne's role as a synthon or precursor in selected synthetic transformations.
- Emphasis on reactions that have achieved 'name reaction' status in organic chemistry.
Main Results:
- Alkynes are extensively utilized in various name reactions, including Sonogashira, Glaser, Friedel-Crafts, Castro-Stephens coupling, Huisgen 1,3-dipolar cycloaddition (Click reaction), and Hetero Diels-Alder reactions.
- The review showcases selected name reactions where alkynes function as key starting materials or precursors.
- Alkynes demonstrate significant versatility as privileged synthons in constructing heterocycles and complex biologically active compounds.
Conclusions:
- Alkynes are indispensable in modern organic synthesis, particularly in well-established name reactions.
- Their application as privileged synthons facilitates the efficient synthesis of diverse molecular architectures.
- The continued exploration of alkyne chemistry promises further advancements in synthetic organic chemistry, pharmacology, and nanotechnology.
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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.
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.
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
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.
Acidity of 1-Alkynes
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
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.