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Direct Synthesis of Mono-α-arylated Ketones from Alcohols and Olefins via Ni-Catalyzed Oxidative Cross-Coupling

Peng-Fei Yang and Wei Shu*

*Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, Guangdong, P. R. China, Email: shuwsustech.edu.cn

P.-F. Yang, W. Shu, Org. Lett., 2020, 22, 6203-6208.

DOI: 10.1021/acs.orglett.0c02340



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Abstract

A Ni-catalyzed dehydrogenative cross-coupling reaction cascade between readily available alcohols and olefins enables a direct synthesis of α-arylated ketones. This cost-effective method provides monoarylated ketones in good yields with exclusive selectivity without using any advanced synthetic intermediates.

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Details

The document discusses a novel method for the direct synthesis of mono-α-arylated ketones from alcohols and olefins using a nickel-catalyzed oxidative cross-coupling reaction. This method addresses the challenges of site-selectivity and overarylation in ketone synthesis. The process involves the dehydrogenation of alcohols to aldehydes, followed by regioselective hydroacylation with olefins. The optimal conditions include using Ni(COD)2, IAd·HCl, and potassium tert-butoxide in a toluene-dioxane mixture at 110°C, yielding α-phenyl ketone in 85% isolated yield. The method is versatile, accommodating various alcohols and olefins, and produces ketones in good yields with broad functional group tolerance. Mechanistic studies indicate that aldehydes are formed catalytically during the reaction. This approach offers a cost-effective and straightforward route to monoarylated ketones, avoiding the use of unstable and expensive aldehydes. The research highlights the importance of nickel's dual catalytic role and the selection of appropriate ligands for achieving high selectivity and efficiency. The findings are significant for the synthesis of ketones, which are crucial intermediates in pharmaceuticals and materials science.


Key Words

hydroacylation, benzylation


ID: J54-Y2020