Recent advances in the application of alkynes in multicomponent reactions
Seyedmohammad Hosseininezhad1, Ali Ramazani1,2
1The Organic Chemistry Research Laboratory (OCRL), Department of Chemistry, Faculty of Science, University of Zanjan Zanjan 45371-38791 Iran hossinichemistry1397@gmail.com M.hosseininezhad@stu.nit.ac.ir aliramazani@gmail.com aliramazani@znu.ac.ir.
Abstract:
Alkynes have two active positions to carry out chemical reactions: C[triple bond, length as m-dash]C and C-H. These two positions are involved and activated in different reactions using different reagents. In this study, we investigated the reactions of alkynes that are involved in multi-component reactions through the C-C and C-H positions and examined the progress and gaps of each reaction by carefully studying the mechanism of the reactions. Firstly, we investigated and analyzed the reactions involving the C[triple bond, length as m-dash]C position of alkynes, including the reactions between derivatives of alkynes with RN3, sulfur compounds (RSO2R', DMSO, S8, DABCO(SO2)2 and DABSO), barbituric acids, aldehydes and amines, COOH, α-diazoesters or ketones, and isocyanides. Then, we examined and analyzed the important reactions involving the C-H position of alkynes and the progress and gaps in these reactions, including the reaction between alkyne derivatives with amines and aldehydes for the synthesis of propargylamines, the reaction between alkynes with CO2 and the reaction between alkynes with CO.
More Related Videos
06:46Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
05:34Efficient Synthesis of Polyfunctionalized Benzenes in Water via Persulfate-promoted Benzannulation of α,β-Unsaturated Compounds and Alkynes
Published on: December 16, 2019
Related Concept Videos
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.
02:34Preparation 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.
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.
02:38Electrophilic 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.
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.
02:47Alkynes 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.