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. 2019 Aug 14;141(32):12464-12469.
doi: 10.1021/jacs.9b04800. Epub 2019 Aug 2.

Stereospecific Synthesis of E-Alkenes through Anti-Markovnikov Hydroalkylation of Terminal Alkynes

Avijit Hazra  1 , Jason Chen  1 , Gojko Lalic  1
Affiliations

Stereospecific Synthesis of E-Alkenes through Anti-Markovnikov Hydroalkylation of Terminal Alkynes

Avijit Hazra et al. J Am Chem Soc. .

Abstract

We have developed a method for stereospecific synthesis of E-alkenes from terminal alkynes and alkyl iodides. The hydroalkylation reaction is enabled by a cooperative action of copper and nickel catalysts and proceeds with excellent anti-Markovnikov selectivity. We demonstrate the broad scope of the reaction, which can be accomplished in the presence of esters, nitriles, aryl bromides, ethers, alkyl chlorides, anilines, and a wide range of nitrogen-containing heteroaromatic compounds. Mechanistic studies provide evidence that the copper catalyst activates the alkyne by hydrocupration, which controls both the regio- and diastereoselectivity of the overall reaction. The nickel catalyst activates the alkyl iodide and promotes cross coupling with the alkenyl copper intermediate.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1.
Scheme 1.
Hydroalkylation of Alkynes
Scheme 2.
Scheme 2.
Scheme 3.
Scheme 3.
Preliminary Results
Scheme 4.
Scheme 4.
Proposed Mechanism
Scheme 5.
Scheme 5.
See this image and copyright information in PMC

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