1734
Click Reaction Assisted By Cu Electro-Oxidation

Sunday, 30 September 2018: 14:40
Universal 10 (Expo Center)
L. Carre-Rangel (Instituto Tecnológico de Tijuana), M. T. Oropeza-Guzman (InstitutoTecnológico de Tijuana), and I. A. Rivero (Instituto Tecnológico de Tijuana)
The click chemistry is a green, selective, qualitative, pH-sensitive and economical approach, suitable characteristics for use in the synthesis of a variety of bioconjugates including peptides, proteins, polysaccharides, etc. The purpose of the click chemistry reactions is to bind two molecular building blocks, selectively and under mild reaction conditions, obtaining high yields, generating only harmless byproducts of reaction and easy to separate by non-chromatographic methods.

In 2002, Sharpless's research group reported the 1,3-dipolar Copper catalyzed Alkyne Azide Cycloaddition (CuAAC) reaction, which is regioselective for the formation of 1,4-disubstituted triazoles, becoming the best known click reaction.The reaction is carried out at room temperature and has high conversions at shorter times, compared to the uncatalyzed (not regioselective) cycloaddition reported by Huisgen in 1963. Other strategies have been reported to perform the cycloaddition of alkynes and azides without the use of a copper catalyst, however, for these reactions the kinetics are slow and do not present regioselectivity. Hence, the process catalyzed by copper is still preferred.

Intending to improve the green chemistry procedure to synthesize triazoles, considering that electrons as redox reactants instead of polluting reducing/oxidizing reagents, it is propose to assist a conventional click reaction by electrochemical methods. Since a metallic species as Cu is relatively easy to oxidize by an electrolysis, the main objective is to generate ionic species of Cu as Cu+1 serving to catalyze the click reaction. For this purpose a suitable electrolytic media as well as a proper electrochemical cell configuration (Cu-working electrode, Ag/AgCl/Cl-(tert-butylalcohol/water) reference electrode and Pt-counter electrode) were used to test the reaction improvement by the in-situ electro-oxidation of Cu.

The synthesis of 1-benzyl-4-phenyl-1H-1,2,3-triazole, 3-(1-benzyl-1H-1,2,3-triazol-4-yl)phenol and 1-benzyl-4-(naphthalen-1-yl)-1H-1,2,3-triazole derivatives via the in-situ preparation of Cu+1 by an electrochemical process, was very efficient, safe and inexpensive, since catalyst was obtained under soft conditions reaction generating extremely small amounts of electrooxidized Cu (~4.3x10-3 mol in one hour).

Conventional and electrochemical methods were compared, the last method yielded 78-90% in one hour of reaction and the conventional method produced only 56-60% at the same time, therefore, the electro-Click reaction is faster and more efficient.