The Huisgen 1,3-dipolar cycloaddition is a powerful reaction, cyclizing an azide with an alkyne to form a 1,2,3-triazole, and has been demonstrated to be tolerant of many functional groups and conditions. Despite the many advances made with the Huisgen cycloaddition, and its famous derivative the copper catalyzed azide/alkyne cycloaddition (CuAAC), there are few examples of the reaction taking place successfully with a metal directly bound to the reactive alkyne/azide. In fact, to our knowledge, there have been no examples of a successful Huisgen cycloaddition utilizing a direct bond to zirconium from the reactive moiety. In this work, we demonstrate the successful formation of a 1,2,3-triazole when reacting Cp2Zr(N3)2 with Si(CH3)3CCH and benzyl acetylene, though the triazole formed does not show evidence for maintaining the Zr-N bond. Interestingly, deuterium studies in THF-d8 show the incorporation of deuterium into the acetylide position, formed through the C-D activation of THF.

Reactions of zirconocene diazide with terminal alkynes: Precatalysts for C-H activation?

ACS Spring 2022

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