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Synlett 2019; 30(19): 2136-2142
DOI: 10.1055/s-0039-1690719
DOI: 10.1055/s-0039-1690719
letter
Copper Aluminate Spinel in Click Chemistry: An Efficient Heterogeneous Nanocatalyst for the Highly Regioselective Synthesis of Triazoles in Water
Financial support from the Shiraz University research council is gratefully acknowledged.Further Information
Publication History
Received: 01 October 2019
Accepted after revision: 03 October 2019
Publication Date:
04 November 2019 (online)
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.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690719.
- Supporting Information
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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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