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Updated: Aug 27, 2025
Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Vinyl cation-mediated intramolecular hydroarylation of alkynes using pyridinium reagents
James C Corcoran1, Rui Guo1, Yue Xia1
1Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA. ym.wang@pitt.edu.
Abstract:
Once considered to be exotic species of limited synthetic utility, vinyl cations have recently been shown to be highly versatile intermediates in a variety of processes. Here, we report a method for the synthesis of aryl-substituted benzocycloheptenes and -hexenes using the hydrotriflate salt of an electron-poor pyridine as a uniquely efficient proton source for a vinyl cation mediated Friedel-Crafts cyclization. The mild conditions made possible by this reagent allowed a range of simple and functionalized alkynes bearing pendant aryl groups to serve as suitable substrates for this scalable and convenient protocol.
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02:35Electrophilic Addition to Alkynes: Hydrohalogenation
02:24Reduction 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.
02:47Alkynes 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.
02:27Preparation 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.
02:40Alkynes 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.
02:38Electrophilic 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.