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Updated: Aug 4, 2026
Preparation of a Corannulene-functionalized Hexahelicene by Copper(I)-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
Nickel-catalyzed intermolecular alkyne insertion into cyclobutanones
Masahiro Murakami1, Shinji Ashida, Takanori Matsuda
1Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan. murakami@sbchem.kyoto-u.ac.jp
Nickel(0) catalysts enable cyclobutanones and alkynes to form cyclohexenones via oxidative cyclization. This reaction inserts alkynes into cyclobutanones, creating valuable six-membered carbocyclic skeletons efficiently.
Area of Science:
- Organic Chemistry
- Organometallic Chemistry
- Catalysis
Background:
- Cyclobutanones are strained four-membered cyclic ketones.
- Alkynes are unsaturated hydrocarbons containing carbon-carbon triple bonds.
- Efficient synthesis of six-membered carbocyclic compounds is crucial in organic chemistry.
Purpose of the Study:
- To develop a novel synthetic route to cyclohexenones.
- To explore the reactivity of cyclobutanones with alkynes using nickel catalysis.
- To achieve formal alkyne insertion into cyclobutanones.
Main Methods:
- Reaction of cyclobutanones with various alkynes.
- Utilizing nickel(0) complexes as catalysts.
- Employing oxidative cyclization and reductive elimination mechanisms.
Main Results:
- Successful synthesis of substituted cyclohexenones from cyclobutanones and alkynes.
- Demonstration of a formal alkyne insertion between the carbonyl and alpha-carbon of cyclobutanones.
- Identification of key mechanistic steps including oxidative cyclization and beta-carbon elimination.
Conclusions:
- Nickel(0)-catalyzed reaction provides an effective method for constructing six-membered carbocyclic rings.
- The reaction offers a new pathway for functionalizing cyclobutanones and alkynes.
- This methodology expands the synthetic utility of cyclobutanones in organic synthesis.
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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.
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