1246847-67-5

Upstream product

• 7438-05-3 1-azidooctane 
• 768-60-5 4-methoxyphenylacetylen 
• 3989-14-8 (4-methoxyphenylethynyl)trimethylsilane 

Relevant academic research and scientific papers

Hydroxyapatite-supported copper(II)-catalyzed azide-alkyne [3+2] cycloaddition with neither reducing agents nor bases in water

Copper(II)-exchanged hydroxyapatite, prepared by ion-exchanging of Ca(II) in calcium hydroxyapatite [Ca10(PO4)6(OH) 2] with Cu(NO3)2 at 70 °C in water, functions as a reusable heterogeneous

General Cycloaddition between a Trimethylsilyl-Capped Alkyne and an Azide Catalyzed by an N-Heterocyclic Carbene-Copper Complex and Pyridine-Biscarboxamide

With an externally provided catalytic amide facilitator and an N-heterocyclic carbene-copper (NHC-Cu) complex, the cycloaddition of an azide and a trimethylsilyl (TMS)-capped alkyne can proceed smoothly. This protocol can be applied to a variety of TMS-capped substrates, with electron-rich alkynes generally giving higher yields and nitroaromatic alkynes giving lower yields. For special applications of this protocol, a substrate containing both a terminal alkyne and a TMS-capped alkyne can sequentially react with different azides without isolation of intermediates; and a macrocyclic product can also be formed efficiently without the complication of polymer formation.

Chelation-assisted, copper(II)-acetate-accelerated azide-alkyne cycloaddition

We described in a previous communication a variant of the popular Cu I-catalyzed azide-alkyne cycloaddition (AAC) process where 5 mol % of Cu(OAc)2 in the absence of any added reducing agent is sufficient to enable the reaction. 2-Picolylazide (1) and 2-azidomethylquinoline (2) were found to be by far the most reactive carbon azide substrates that convert to 1,2,3-triazoles in as short as a few minutes under the discovered conditions. We hypothesized that the abilities of 1 and 2 to chelate CuII contribute significantly to the observed high reaction rates. The current work examines the effect of auxiliary ligands near the azido group other than pyridyl for CuII on the efficiency of the Cu(OAc)2-accelerated AAC reaction. The carbon azides capable of binding to the catalytic copper center at the alkylated azido nitrogen in a chelatable fashion were indeed shown to be superior substrates under the reported conditions. The chelation between carbon azide 11 and CuII was demonstrated in an X-ray single-crystal structure. In a limited set of examples, the ligand tris(benzyltriazolylmethyl) amine (TBTA), developed by Fokin et al. for assisting the original Cu I-catalyzed AAC reactions, also dramatically enhances the Cu(OAc)2-accelerated AAC reactions involving nonchelating azides. This observation leads to the hypothesis of an additional effect of chelating azides on the efficiencies of Cu(OAc)2-accelerated AAC reactions, which is to facilitate the rapid reduction of CuII to highly catalytic CuI species. Mechanistic studies on the AAC reactions with particular emphasis on the role of carbon azide/copper interactions will be conducted based on the observations reported in this work. Finally, the immediate utility of the product 1,2,3-triazole molecules derived from chelating azides as multidentate metal coordination ligands is demonstrated. The resulting triazolyl-containing ligands are expected to bind with transition metal ions via the N(2) nitrogen of the 1,2,3-triazolyl group to form nonplanar coordination rings. The CuII complexes of bidentate T1 and tetradentate T6 and the ZnII complex of T6 were characterized by X-ray crystallography. The structure of [Cu(T1)2(H2O) 2](ClO4)2 reveals the interesting synergistic effect of hydrogen bonding, π-π stacking interactions, and metal coordination in forming a one-dimensional supramolecular construct in the solid state. The tetradentate coordination mode of T6 may be incorporated into designs of new molecule sensors and organometallic catalysts.