Liu Xu, Liu Ruoyu, Qiu Jiaxing, Cheng Xu, Li Guigen
Institute of Chemistry and Biomedical Sciences, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, National Demonstration Center for, Experimental Chemistry Education, Nanjing University, Nanjing, 210023, China.
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou, 310032, China.
Angew Chem Int Ed Engl. 2020 Aug 10;59(33):13962-13967. doi: 10.1002/anie.202005765. Epub 2020 Jun 4.
We report a method for the electrochemical deuteration of α,β-unsaturated carbonyl compounds under catalyst- and external-reductant-free conditions, with deuteration rates as high as 99 % and yields up to 91 % in 2 h. The use of graphite felt for both the cathode and the anode was key to ensuring chemoselectivity and high deuterium incorporation under neutral conditions without the need for an external reductant. This method has a number of advantages over previously reported deuteration reactions that use stoichiometric metallic reductants. Mechanistic experiments showed that O evolution at the anode not only eliminates the need for an external reductant but also regulates the pH of the reaction mixture, keeping it approximately neutral.
我们报道了一种在无催化剂和外部还原剂的条件下对α,β-不饱和羰基化合物进行电化学氘代的方法，氘代率高达99%，在2小时内产率可达91%。使用石墨毡作为阴极和阳极是在中性条件下无需外部还原剂就能确保化学选择性和高氘掺入率的关键。与先前报道的使用化学计量金属还原剂的氘代反应相比，该方法具有许多优点。机理实验表明，阳极处的析氧反应不仅消除了对外部还原剂的需求，还调节了反应混合物的pH值，使其保持在近似中性。
