Key Non‐Metal Ingredients for Cu‐catalyzed “Click” Reactions in Glycerol: Nanoparticles as Efficient Forwarders

Abstract

Abstract:The effect of long-alkyl chain amines in CuI-assisted azide-alkyne cycloadditions of terminal alkynes with organic azides in glycerol and other eco-friendly solvents (water, ethanol) has been examined. The presence of these additives favors the in situ formation of Cu(I)-based nanoparticles and results in an increase of reactivity. In glycerol, liquid phase Transmission Electron Microscopy (TEM) analyses enabled by the negligible vapor pressure of this solvent proved that Cu(I) nanoparticles are responsible of the observed catalytic activity. The wide variety of alkynes and azides where this effect has been investigated (14 combinations) confirms the role played by these additives in Cu-catalysed Huisgen cycloadditions.

Synthetic Organic Transformations of Transition‐Metal Nanoparticles as Propitious Catalysts: A Review

“…In 2016, Gómez group probed the effect of non-metal ingredients in the copper-iodide nanoparticle catalyzed "click" reactions in glycerol as solvent (Scheme 51). [37] They examined the effect of long-alkyl-chain amines in the formation of NPs of CuI. Small amounts (5 mol%) of primary, secondary, or tertiary amines containing C 8 , C 11 , or C 18 carbon chains (CuI/amine ratio = 1/1 or 1/5) promoted the room temperature cycloaddition of terminal olefins 109 with substituted azides 110 to afford 1,4-disubstitued 1,2,3-triazoles 111.…”

“…In 2016, Gómez group probed the effect of non‐metal ingredients in the copper‐iodide nanoparticle catalyzed “click” reactions in glycerol as solvent (Scheme ) . They examined the effect of long‐alkyl‐chain amines in the formation of NPs of CuI.…”

Metal-based nanoparticles dispersed in glycerol: An efficient approach for catalysis

“…With the aim of making easier and pursuing a "click" methodology [67], we studied the CuAAC reaction using CuI in glycerol as catalytic precursor and in the absence of any Lewis base, for the benchmark reaction between phenylacetylene and benzyl azide [68].…”

Introducing Glycerol as a Sustainable Solvent to Organolithium Chemistry: Ultrafast Chemoselective Addition of Aryllithium Reagents to Nitriles under Air and at Ambient Temperature

“…[9] Obtained as am ajor by-product of the biodiesel industry, [10] glycerol (Gly)i saparticularly appealing green solvent. [12] Nevertheless, despite these key advantages, Gly has never been used as as olvent in organolithium chemistry,p robably as ac onsequence of the common assumption that these polar reagents will rapidly decompose in this solventthrough reactionwith its acidic alcohol groups. [12] Nevertheless, despite these key advantages, Gly has never been used as as olvent in organolithium chemistry,p robably as ac onsequence of the common assumption that these polar reagents will rapidly decompose in this solventthrough reactionwith its acidic alcohol groups.…”