Blue Light Induced Difluoroalkylation of Alkynes and Alkenes
Kangkui Li1, Xuexin Zhang1, Jingchao Chen1
1Institution Key Laboratory of Chemistry in Ethnic Medicinal Resources (Yunnan Minzu University) , State Ethnic Affairs Commission & Ministry of Education , Kunming , 650500 , China.
Abstract:
The difluoroalkylation of alkynes and alkenes by direct photoexcitation of ethyl difluoroiodoacetate is described. Under catalyst- and oxidant-free conditions, iododifluoroalkylation and hydrodifluoroalkylation products were generated from alkynes, and difluoroalkylation products were prepared from alkenes. This methodology provides a streamlined access to difluoroalkylated organic compounds starting from simple alkynes or alkenes.
Related Concept Videos
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: 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.
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.
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: 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: Hydrohalogenation


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