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Visible-Light-Mediated Vicinal Difunctionalization of Activated Alkynes with Boronic Acids: Substrate-Controlled
Sabyasachi Manna1, Kandikere Ramaiah Prabhu1
1Department of Organic Chemistry, Indian Institute of Science, Bangalore 560012, Karnataka India.
Abstract:
A visible-light-mediated difunctionalization of activated alkynes with boronic acid is unveiled to synthesize 3-alkylated coumarins and unsaturated spiro-lactones. The substituent at the para-position of the aryl ring of aryl alkynoate plays a pivotal role in the selective formation of chain-alkylated coumarins or spirocyclic compounds under mild conditions. The reaction employs a hypervalent iodine reagent and ruthenium photocatalyst. The spiro-lactones thus obtained were subjected to another novel mode of visible-light-mediated radical addition cascade cyclization (RACC) to access various new fused spirocyclic compounds.
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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.
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.
Hydroboration-Oxidation of Alkenes