Dehydrogenative desaturation-relay via formation of multicenter-stabilized radical intermediates

Yaping Shang, Xiaoming Jie (), Krishna Jonnada, Syeda Nahid Zafar and Weiping Su ()
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Yaping Shang: Chinese Academy of Sciences
Xiaoming Jie: Chinese Academy of Sciences
Krishna Jonnada: Chinese Academy of Sciences
Syeda Nahid Zafar: Chinese Academy of Sciences
Weiping Su: Chinese Academy of Sciences

Nature Communications, 2017, vol. 8, issue 1, 1-8

Abstract: Abstract In organic molecules, the reactivity at the carbon atom next to the functional group is dramatically different from that at other carbon atoms. Herein, we report that a versatile copper-catalyzed method enables successive dehydrogenation or dehydrogenation of ketones, aldehydes, alcohols, α,β-unsaturated diesters, and N-heterocycles to furnish stereodefined conjugated dienecarbonyls, polyenecarbonyls, and nitrogen-containing heteroarenes. On the basis of mechanistic studies, the copper-catalyzed successive dehydrogenation process proceeds via the initial α,β-desaturation followed by further dehydrogenative desaturation of the resultant enone intermediate, demonstrating that the reactivity at α-carbon is transferred through carbon–carbon double bond or longer π-system to the carbon atoms at the positions γ, ε, and η to carbonyl groups. The dehydrogenative desaturation–relay is ascribed to the formation of an unusual radical intermediate stabilized by 5- or 7,- or 9-center π-systems. The discovery of successive dehydrogenation may open the door to functionalizations of the positions distant from functional groups in organic molecules.

Date: 2017
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DOI: 10.1038/s41467-017-02381-8

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