Copper Aluminate Spinel in Click Chemistry: An Efficient Heterogeneous Nanocatalyst for the Highly Regioselective Synthesis of Triazoles in Water

Abstract

An expeditious protocol for the one-pot synthesis of 1,4-disubstituted (β-hydroxy)-1,2,3-triazoles in an aqueous medium has been developed using copper aluminate nanoparticles. This heterogeneous catalytic system was found to drive a multicomponent click reaction between organic azides (generated in situ from epoxides or halides) and terminal aliphatic or aromatic alkynes in up to 96% yield without the need for a reducing agent. Structurally diverse 1,2,3-triazoles were synthesized in good to excellent yields, and the catalyst could be easily separated by simple filtration, recycled, and reused in six subsequent cycles.

Key words

click chemistry - copper catalysis - triazoles - epoxides - azides - alkynes

• References and Notes

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• 20 1,2,3-Triazoles; General ProcedureIn a 10 mL round-bottomed flask, the alkyl halide or epoxide (1 mmol), terminal alkyne (1.1 mmol), and NaN₃ (1.2 mmol) were mixed and stirred in H₂O (3 mL) in the presence of the CuAl₂O₄ catalyst (0.005g) at 90 °C. When the reaction was complete (TLC; hexane–EtOAc), the catalyst was collected by simple filtration. The filtrate was diluted with H₂O (5 mL) and extracted with EtOAc (3 × 10 mL). The combined organic phases were washed with brine, dried (Na₂SO₄), and concentrated under reduced pressure. The resulting residue was purified by column chromatography (silica gel, hexane–EtOAc).4-({4-[(4-Benzylphenoxy)methyl]-1H-1,2,3-triazol-1-yl}methyl)benzonitrile (3l)Yellow solid; yield: 372 mg (89%); mp 63–65 °C. IR (KBr): 3031, 2923, 2360, 2240, 1612, 1512, 1458, 1334, 1234, 1110, 1002, 833, 725 cm^–1. ¹H NMR (250 MHz, CDCl₃): δ = 4.93 (s, 2 H), 5.58 (s, 2 H), 5.68 (s, 2 H), 6.69 (dd, J = 7.5, 2.5 Hz, 2 H), 6.88 (dd, J = 10.1, 5.4 Hz, 2 H), 7.27–7.34 (m, 5 H), 7.57 (dd, J = 7.5, 2.5 Hz, 2 H), 7.64 (dd, J = 7.5, 2.5 Hz, 2 H), 7.75 (s, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 41.09, 53.37, 58.25, 112.31, 114.80, 123.16, 126.13, 128.20, 128.86, 130.00, 130.16, 132.87, 134.13, 135.04, 139.87, 141.46, 145.08, 156.55.4-[(4-Benzylphenoxy)methyl]-1-(3-fluorobenzyl)-1H-1,2,3-triazole (3m)Yellow solid; yield: 369 mg (90%); mp 59–61 °C. IR (KBr): 3070, 2916, 2353, 1697, 1512, 1450, 1250, 1049, 732, 694, 594 cm^–1. ¹H NMR (250 MHz, CDCl₃): δ = 3.82 (s, 2 H), 5.07 (s, 2 H), 5.40 (s, 2 H), 6.65 (dd, J = 5.3, 2.5 Hz, 1 H), 6.84–6.95 (m, 3 H), 6.97–7.02 (m, 3 H), 7.06–7.11 (m, 4 H), 7.14–7.17 (m, 2 H), 7.45 (s, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 41.14, 53.32, 62.00, 114.71–115.80 (m, 2 C), 126.18, 128.61, 128.97, 130.08, 130.90, 134.07, 137.33, 141.61, 144.68, 156.76, 161.73–164.19 (d, J = 248.5 Hz, 1 C).2-{4-[(4-Benzylphenoxy)methyl]-1H-1,2,3-triazol-1-yl}-1-phenylethanol (5g)White solid; yield: 351 mg (83%); mp 64–66 °C. IR (KBr): 3309, 3062, 2916, 2360, 2245, 2098, 1951, 1890, 1604, 1504, 1450, 1342, 1242, 1049, 910, 840 cm^–1. ¹H NMR (250 MHz, CDCl₃): δ = 3.89–3.93 (m, 2 H), 4.10–4.22 (m, 1 H), 4.49–4.64 (m, 1 H), 5.13–5.15 (m, 2 H), 5.57–5.65 (m, 1 H), 6.84–6.90 (m, 2 H), 7.16–7.35 (m, 12 H), 7.53–7.56 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 41.11, 61.99, 64.77, 67.30, 114.83, 123.76, 126.12, 127.25, 128.54, 128.90, 128.96, 129.14, 130.02, 134.04, 136.08, 141.50, 144.05, 156.66.
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