Design and Applications of an Efficient Amphiphilic “Click” Cu^I Catalyst in Water

Abstract

The copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) using the conventional Sharpless-Fokin catalyst that consists of CuSO 4 + Na ascorbate, the most well-known and used "click" reaction, is considerably accelerated by the addition of a tris(triazolyl)-polyethylene glycol (tris-trz-PEG) amphiphilic ligand in water under ambient conditions. Only parts-per-million Cu I were necessary to reach quantitative yields with TON up to 86000 and TOF 3600 h -1 . The ligand was fully recycled, and the catalyst reused at least 6 times without decomposition. Large-scale syntheses were also successfully achieved with 93 % yield. The catalyst was applied to the efficient synthesis of various useful functional products with medicinal, catalytic, targeting, and labeling properties.

Nuclear Magnetic Resonance Spectroscopy Investigations of Naphthalene-Based 1,2,3-Triazole Systems for Anion Sensing

“…The binding pocket is created by the phenolic -OH and triazole Csp2-H site (Scheme 2). Detailed NMR investigations (1) showed the structural skeleton of NpTP; (2) displayed the binding interaction with F − ; and (3) revealed the Bypassing complicated synthetic steps, the 1,2,3-triazole chemosensors is accessed in one step with an azide-alkyne cycloaddition utilizing the most well-known "Click" reaction [41][42][43][44][45][46]. With this approach, the recognition core can be easily retained while the signaling units are readily modified using commercially available precursors.…”

Highly Stable Copper Nanoparticles Linked to Organic Frameworks as Recyclable Catalyst for Three‐Component Click Cycloaddition in Water

“…Recently reported catalysts for click reactions with high TOF include, dendrimer nanoreactor for part‐per‐million Cu 1 catalyst (TON =510000, TOF=21200 h −1 ), amphiphilic Cu 1 catalyst (TON=86000, TOF 3600 h −1 ) for two component click reaction and alumina supported CuI (TON=495, TOF=4950 h −1 ) for three component click reactions. The TOF and TON values obtained with our catalyst for both two‐component (Table ) and three‐component reactions (Table , Table S6 and Table S7) are comparable and even higher than the recently reported values…”

“…Recently reported catalysts for click reactions with high TOF include, dendrimer nanoreactor for part-per-million Cu 1 catalyst (TON = 510000, TOF = 21200 h À1 ), [88] amphiphilic Cu 1 catalyst (TON = 86000, TOF 3600 h À1 ) [89] for two component click reaction and alumina supported CuI (TON = 495, TOF = 4950 h À1 ) [90] for three component click reactions. The TOF and TON values obtained with our catalyst for both two-component (Table 1) and threecomponent reactions ( Table 2, Table S6 and Table S7) are comparable and even higher than the recently reported values It is a well-accepted principle that supported nanoparticle catalysts on supports are better than bulk metal catalysts owing to the large surface to volume ratio and the distribution of the particles on the support surface.…”

Copper(I)‐Chelated Cross‐Linked Cyclen Micelles as a Nanocatalyst for Azide‐Alkyne Cycloaddition in Both Water and Cells

“…The dendrimers, benefited from their precise molecular weight, spherical nanostructure, functionalized exterior, and superstability, can take the advantages of both heterogeneous and homogenous catalysts, and seem to be a more superior catalyst carrier. In this regard, Astruc and coworkers did seminal studies, and in some of them the copper dosage was even reduced to parts‐per‐million (ppm) level and could be recycled many times . However, although these dendrimer supported metal catalysts are promising, the dendrimer carriers themselves require complex chemical synthesis.…”