Mechanism of Copper(I)-Catalyzed 5-Iodo-1,2,3-triazole Formation from Azide and Terminal Alkyne

The Journal of Organic Chemistry
David N BarsoumLei Zhu

Abstract

5-Iodo-1,2,3-triazole (iodotriazole) can be prepared from a copper(I)-catalyzed reaction between azide and terminal alkyne in the presence of an iodinating agent, with 5-protio-1,2,3-triazole (protiotriazole) as the side product. The increasing utilities of iodotriazoles in synthetic and supramolecular chemistry drive the efforts in improving their selective syntheses based on a sound mechanistic understanding. A routinely proposed mechanism takes the cue from the copper(I)-catalyzed azide-alkyne cycloaddition, which includes copper(I) acetylide and triazolide as the early and the late intermediates, respectively. Instead of being protonated to afford protiotriazole, an iodinating agent presumably intercepts the copper(I) triazolide to give iodotriazole. The current work shows that copper(I) triazolide can be iodinated to afford iodotriazoles. However, when the reaction starts from a terminal alkyne as under the practical circumstances, 1-iodoalkyne (iodoalkyne) is an intermediate while copper(I) triazolide is bypassed on the reaction coordinate. The production of protiotriazole commences after almost all of the iodoalkyne is consumed. Using (1)H NMR to follow a homogeneous iodotriazole forming reaction, the rapid formation of ...Continue Reading

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Citations

Feb 22, 2016·Bioorganic & Medicinal Chemistry Letters·Audrey HottinJean-Bernard Behr
Mar 8, 2019·Chemical Communications : Chem Comm·Suguru YoshidaTakamitsu Hosoya
Mar 16, 2018·Scientific Reports·Jacek MularskiRobert Musiol
May 22, 2018·Chemical Science·Joseph L HowardDuncan L Browne
May 25, 2016·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Lei ZhuRonald J Clark
Mar 2, 2021·Chemical & Pharmaceutical Bulletin·Ryosuke KoriSatoshi Yokoshima
Dec 8, 2020·The Journal of Organic Chemistry·Elisabeth SitteMathias O Senge

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