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

Journal of the American Chemical Society
Avijit HazraGojko Lalic

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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Citations

Oct 1, 2021·Journal of the American Chemical Society·Mitchell T Lee, Gojko Lalic
Nov 3, 2021·Organic Letters·Chuan-Jin HouStephen L Buchwald
Nov 3, 2021·Angewandte Chemie·Anne K RavnTroels Skrydstrup

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