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Copper-Catalyzed Desaturation of Lactones, Lactams, and Ketones under pH-Neutral Conditions

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journal contribution
posted on 05.09.2019, 15:38 by Ming Chen, Guangbin Dong
A copper-catalyzed desaturation method that is suitable for converting lactones, lactams, and cyclic ketones to their α,β-unsaturated counterparts is reported. The reaction does not require strong base/acid or sulfur/selenium reagents and can be carried out through a simple one-step operation. The protocol uses inexpensive catalysts and reagents and exhibits excellent scalability and functional group tolerance. Notably, tert-butyl alcohol is the only stoichiometric byproduct produced, and overoxidation is not observed. The reaction mechanism has been investigated through control experiments, deuterium labeling, radical clock, electron paramagnetic resonance, high-resolution mass spectrometry, and kinetic studies. The data obtained are consistent with a reaction pathway involving reversible α-deprotonation by a Cu­(II)–OtBu species followed by further oxidation of the resulting Cu enolate.