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Microwave‐Promoted Metal‐Free α‐Alkylation of Ketones with Cycloalkanes through Cross‐Coupling of C(sp3)−H Bonds

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A MWI-promoted α-alkylation of ketones by using cycloalkanes as the alkylating agents under metal-free conditions is presented. Mechanistically, this alkylation involves a TBP-initiated and MWI-assisted formation of the required cycloalkyl… Click to show full abstract

A MWI-promoted α-alkylation of ketones by using cycloalkanes as the alkylating agents under metal-free conditions is presented. Mechanistically, this alkylation involves a TBP-initiated and MWI-assisted formation of the required cycloalkyl radical and the α-ketone carbon radical followed by their selective cross coupling. To our knowledge, this should be the first example in which simple ketones and 1,3-diketones were efficiently alkylated with cycloalkanes via a cross-dehydrogenative coupling of C(sp3)−H bonds in the absence of any metal catalyst. Compared with literature methods, this new alkylation protocol has advantages such as cheap and abundant substrates, free of metal catalyst, good atom-economy and sustainability. As a further aspect, the substituted ketone obtained herein was found to be valuable intermediate for the preparation of the synthetically and biologically valuable tri-substituted alkene.

Keywords: coupling sp3; sp3 bonds; alkylation; metal free; cross coupling; alkylation ketones

Journal Title: Asian Journal of Organic Chemistry
Year Published: 2017

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