A highly efficient copper(i) catalyst for the 1,3-dipolar cycloaddition of azides with terminal and 1-iodoalkynes in water: regioselective synthesis of 1,4-disubstituted and 1,4,5-trisubstituted 1,2,3-triazoles

Micellar promoted multi-component synthesis of 1,2,3-triazoles in water at room temperature

“…Similarly the reaction between allyl bromide, propargyl dimethyl malonate and sodium azide was more efficient with SLS and TPGS-750-M with respect to the use of pure water (Table 4, entry 16). The reaction of allyl bromide with several aromatic alkynes in SLS as well as in TPGS-750-M yielded quantitative formation of the corresponding triazoles in 30 min, while in pure water the reactivity was much lower especially with less substituted aromatic alkynes (Table 4, entries [17][18][19]. For the highly reactive alkynes reported in Table 4, entries 20 and 21, the reaction was carried out with only 0.5 mol% 1 for 15 minutes at rt observing good to excellent triazole formation in the presence of the selected surfactants while the reaction did not occur in pure water.…”

“…(3) (PTA = 1,3,5-triaza-7-phosphaadamantane) 19 or nitrogen ligands like polytriazoles and tris(2-aminoethyl)amine derivatives (tren) could be employed, usually of the order of 1 mol%. Cu(I) complexes of the type [(NHC)CuX] (NHC = N-heterocyclic carbene, X = halogen) developed by Nolan were found to greatly accelerate the reaction, 20,21 while subsequent bis-carbenic complexes like the heteroleptic bis(N-heterocyclic carbene)-copper(I) complexes developed by Cazin and collaborators 22 as well as ring-expanded carbene ligands 23 showed interesting catalytic activities.…”

SO3Cu‐Carbon: A Novel Heterogeneous Catalyst for the Synthesis of β‐Hydroxy 1,2,3‐Triazoles by One Pot Cycloaddition Reaction

“…Click reaction was carried out by several homogeneous catalysts such as, CuSO 4 /sodium ascorbate/H 2 O, CuI/PEG‐400, and Cu(OAc) 2 /H 2 O, Cu(PPh 3 )NO 3 , PTA‐iminophosphorane, nitrogen containing ligands [(NHC)CuX] exhibiting higher selectivity and activity. However, some of these catalysts suffer high metal loading, difficult to recover along with some metal contaminates in the end product.…”

Metal-Catalyzed Intra- and Intermolecular Addition of Carboxylic Acids to Alkynes in Aqueous Media: A Review

“…On the other hand, based on the capability of copper salts to promote the conjugate alkynylation of electron-deficient olefins, the (Z)-γ-alkylidene butyrolactones 30 could be synthesized in a one-pot manner starting from the corresponding terminal alkynes and the 5-alkylidene-Meldrun's acids 29, via in situ formation of the corresponding propargylic Meldrun's Taking advantage of the ability of the dinuclear iminophosphorane-palladium(II) complex 4 to promote the fast and selective transformation of bispropargylic carboxylic acids 5 into enol-lactones 6 (Scheme 4), García-Álvarez and co-workers could set up an unprecedented one-pot tandem process combining the aforementioned reaction with a copper-catalyzed 1,3-dipolar cycloaddition of azides with the terminal alkyne arm of the enol-lactone products (Scheme 16) [30]. To promote the 1,3-dipolar cycloaddition step the polymeric Cu(I) catalyst [Cu{µ 2 -N,S-(PTA)=NP(=S)(OEt) 2 }] x [SbF 6 ] x (27) containing the same hydrophilic iminophosphorane ligand [63], in combination with the 2,6-lutidine base, was employed. The tandem process proceeded in pure water under mild conditions, affording the bicyclic triazol-enol-lactones 28 in excellent yields after a simple extraction with diethyl ether (no chromatographic purification was needed).…”

“…To promote the 1,3-dipolar cycloaddition step the polymeric Cu(I) catalyst [Cu{µ 2 -N,S-(PTA)=NP(=S)(OEt)2}]x[SbF6]x (27) containing the same hydrophilic iminophosphorane ligand [63], in combination with the 2,6-lutidine base, was employed. The tandem process proceeded in pure water under mild conditions, affording the bicyclic triazol-enol-lactones 28 in excellent yields after a simple extraction with diethyl ether (no chromatographic purification was needed).…”