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A catalytically relevant intermediate in the synthesis of cyclic polymers from alkynes
Christopher D Roland1, Tianyu Zhang1, Sudarsan VenkatRamani1
1University of Florida, Department of Chemistry, Center for Catalysis, P.O. Box 117200, Gainesville, FL 32611, USA. veige@chem.ufl.edu.
Abstract:
A tungsten metallacyclopentadiene complex is generated upon treating a trianionic pincer tungsten alkylidyne with dipropargyl fluorene. The metallacyclopentadiene initiates the polymerization of alkynes to give cyclic polyacetylenes via ring expansion polymerization (REP).
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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.
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.
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.
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.
Nomenclature of Alkynes
Free-Radical Chain Reaction and Polymerization of Alkenes