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Cationic cyclization reactions with alkyne terminating groups: a useful tool in biomimetic synthesis
Olaya García-Pedrero1, Félix Rodríguez1
1Instituto Universitario de Química Organometálica "Enrique Moles", Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Oviedo, Julián Clavería, 8, Oviedo-33006, Spain. frodriguez@uniovi.es.
Abstract:
Cyclization reactions through cationic intermediates have become a highly valuable tool in organic synthesis. The use of alkynes as the terminating group in this type of cationic process offers wide synthetic possibilities because this group can serve as a precursor of different functionalities. This article shows relevant examples of cationic cyclization reactions with alkynes as terminating groups with the intention of demonstrating the potential of this type of process, particularly in the context of biomimetic synthesis of natural products.
Related Concept Videos
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.
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.
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.
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.
α-Alkylation of Ketones via Enolate Ions

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